MBS

OBLIGATIONS

National Bureau of Standards

Library, N.w. Bldg

may i 2 1965

A111D5 14bOflO

& TECH R.I.C.

NSRDS-NBS 2

/nsrds-nb^ 1 "102146086

QC100 .U573_V2.1965 G.2 NBS-PUB-C 1964 Thermal Properties

Of Aqueous Uni-univalent

Electrolytes

U.S. DEPARTMENT OF COMMERCE

NATIONAL BUREAU OF STANDARDS
THE NATIONAL BUREAU OF STANDARDS

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UNITED STATES DEPARTMENT OF COMMERCE • John T. Connor, Secretary

NATIONAL BUREAU OF STANDARDS • A. V. Astin, Director

Thermal Properties of

Aqueous Uni-univalent Electrolytes

Vivian Barfield Parker

NSRDS-NBS 2

»

\ National Standard Reference Data Series

National Bureau of Standards 2

(Category 5 —Thermodynamic and Transport Properties)

Issued April 1, 1965

For sale by the Superintendent of Documents, U.S. Government Printing Office Washington, D.C., 20402 - Price 45 cents

Foreword

In 1963 the President’s Office of Science and Technology established the National Standard

Reference Data System to ensure that the technical community of the United States has maximum

access to compilations of critically evaluated data in the physical sciences. The National Bureau

of Standards was assigned administrative responsibility for this Government-wide activity.

The National Bureau of Standards, as well as other groups both in this country and abroad,

has been active in the compilation of standard reference data for many years. However, in view

of the great accumulation of unevaluated data, the accelerated production of new data, the known

time lag in incorporating these data into critically evaluated compilations, and the urgent needs of

the scientific and technical community, it was decided by the Federal Council for Science and

Technology that a substantially greater effort, planned and coordinated on a national basis, was

needed. The National Standard Reference Data System (NSRDS) is the outgrowth of that decision.

The NSRDS is conducted as a decentralized operation across the country, with central coordination by the NBS. It comprises a complex of data centers and other activities, carried on in

government agencies, academic institutions, and non-government laboratories. The independent

operational status of existing critical data projects is maintained and encouraged. The activities

of data centers which are components of the NSRDS include the preparation of compilations of

critically evaluated data, the preparation of critical reviews of the quantitative state of knowledge

in a specialized area, and computations of useful functions derived from standard reference data.

The present publication is considered to be a product of the National Standard Reference Data

System activities at the NBS. It consists of a compilation of critically evaluated data on the thermodynamic properties of aqueous uni-univalent electrolytes, prepared as one of the continuing projects of the NBS Thermochemistry Section.

A. V. Astin, Director.

Ill
Preface

Since 1940 the National Bureau of Standards has maintained in its Thermochemistry Section

a program on the collection, analysis, and evaluation of chemical thermodynamic data on chemical

substances. One of the important areas of consideration has been the thermochemistry of aque- ous electrolyte solutions. Because of the comparatively regular behavior of dilute univalent electrolyte solutions in water, as predicted by classical theoretical considerations, one can establish

consistent values for the heats and free energies of formation and entropies of the hypothetical

single-ion species, once a value for one particular ion is assigned.

As part of the planned total review of the available chemical thermodynamic data, a systematic

review of the heat-capacity, heat-of-solution, and heat-of-dilution data on simple 1-1 electrolytes

has been made. From the analysis of these data, tables of selected “best” values of “apparent”

heat capacities, and heats of dilution are given, as well as selected values of the heats of solution

to infinite dilution. Also included is a review of data on the heats of neutralization of monobasic

acids which has led to a selected “best” value for the heat of ionization of water.

The author wishes to acknowledge the many stimulating and fruitful discussions with

D. D. Wagman and W. H. Evans of the Thermochemistry Section. The continued financial assist- ance by the Division of Research of the U.S. Atomic Energy Commission is also gratefully

acknowledged.

Vivian B. Parker.

iv
Contents

Page Foreword Ill Preface iv

I. Introduction 1

II. Units of energy and constants 2

III. Uncertainties 2

IV. The apparent molal heat capacity 2

V. Heats of dilution 10

VI. Heat of neutralization 19

VII. Heat of solution at infinite dilution 20

VIII. Review papers 33

IX. References 34

X. Tables 41

List of Figures

Figure I. The apparent molal heat capacity of KC1 at 25 °C 8

Figure II. The apparent molal heat capacity: acids and lithium compounds 8

Figure III. The apparent molal heat capacity: ammonium and sodium compounds 8

Figure IV. The apparent molal heat capacity: potassium, rubidium, and cesium com- pounds 9

Figure V. The apparent molal heat capacity: the oxyanions of hydrogen, sodium and

potassium 9

Figure VI. The apparent molal heat capacity: the chlorides 9

Figure VII. The apparent molal heat capacity: carboxylates 9

Figure VIII. The apparent molal heat capacity: partially ionized compounds 9

Figure IX. The chord area plot for NaCl at 25 °C 17

Figure X. The relative apparent molal enthalpy: acids and ammonium and lithium

compounds 18

Figure XI. The relative apparent molal enthalpy: sodium compounds 18

Figure XII. The relative apparent molal enthalpy: potassium, rubidium and cesium

compounds 18

Figure XIII. The relative apparent molal enthalpy: the hydroxides and chlorides 18

Figure XIV. The relative apparent molal enthalpy: concentrated solutions 19

V

Thermal Properties of Aqueous Uni-univalent Electrolytes

Vivian Barfield Parker

The available specific heat, heat of dilution, and heat of solution data for aqueous solutions of uni-univalent electrolytes have been critically reviewed and tables of selected “best” values at 25 °C

prepared. In addition, the neutralization data have been critically reviewed in order to obtain the “best” value, 13,345 cal/mole, for the heat of ionization of water at 25 °C. The electrolytes reviewed include the hydroxides, halides and oxyhalides, nitrates and nitrites, formates and acetates, cyanides, cyanates and thiocyanates, and permanganates of hydrogen, ammonium and the methyl ammonium derivatives, silver, and the alkali metals.

I. Introduction

The data on the thermal properties of aqueous

uni-univalent electrolytes have been critically re- viewed by Rossini [1, 2, 3, 4, 5],

1 Bichowsky and

Rossini [6], Rossini et al. [7], Harned and Owen

[8, 9], Pitzer and Brewer [10], Britske et al. [11],

Lange and Robinson [12], and Lange and Monheim

[13]. In view of the current program of the Thermochemistry Section on the revision of the tables of

Selected Values of Chemical Thermodynamic

Properties of chemical substances, it was felt advisable to re-examine all the available data on the

thermal properties of the aqueous uni-univalent

electrolytes and select systematically the most

consistent set of values. It is hoped that this re- view, in addition to making available the experimental data, will serve to indicate areas where the

data are inadequate or completely nonexistent.

The terminology and conventions used are those

of Lewis and Randall [14], Lewis, Randall, Pitzer,

and Brewer [10], Rossini [2, 3, 4], Harned and Owen

[9], and Glasstone [15]. A summary of the terms

used and their definitions follows:

<DC is the apparent molal heat capacity of the

solute, equal to [(1000 + mM2)C~ 1000 C°]lm where

C and C° are the specific heats (per unit mass) of

the solution and pure solvent, respectively, m is the

molality, and M2 is the molecular weight of the

solute.

A//(jqn , the integral heat of dilution, is the change

in enthalpy, per mole of solute, when a solution of

concentration mi is diluted to a final finite concentration m2 . If the dilution is carried out by the addition of an

infinite amount of solvent, so that the final solution

is infinitely dilute, the enthalpy change is the in- tegral heat of dilution to infinite dilution. Since

<I>l, the relative apparent molal enthalpy, is equal

to and of opposite sign to this, only <I>l is referred

to here when discussing dilution to infinite dilution.

L2 is the relative partied molal enthalpy of the

solute in the given solution, equal to <I>l+ \mxl2

L\ is the relative partied molal enthalpy of the

solvent in the given solution, equal to — (Mim312 I2000){d<t>udm112

), where Mi is the molecular weight

of the solvent. It is edso the partial or differential

heat of dilution and may be defined as the change

> Figures in brackets indicats the literature references on pages 34-41.

in enthalpy per mole of solvent when it is added to a large volume of the solution at the given

concentration.

J2 is the relative partial molal heat capacity of the

solute, jjqual to C2 — C2, which is equal to (dZ^/dT)?,

where C2 is equal to <I>c+ \ m1,2 (dScldm112

) and

is equal to <!>£. <D£ is the value of the apparent molal heat capacity

of the solute at infinite dilution. It is not to be con- fused with the heat capacity of the pure solvent.

The limiting slopes of the apparent molal properties were taken as two thirds the limiting slopes

for the partial molal properties given by Harned

and Owen [9]. A7/Soin is the total or integral heat of solution of one mole of solute to form a solution of concentration m. It is equal to {Hm — 55.506//i — m//2 )/m,

where Hm is the enthalpy of the solution, and Hi

and H2 are the molar enthalpies of the pure solvent

and solute, respectively.

The partial or differential heat of solution is the

increase in enthalpy per mole of solute when it is dissolved in a large volume of solution at a concentration m, so that there is no appreciable change in

the latter. It is equal to L2 — L2 where L2 is the

relative partial molal enthalpy of the pure solute.

AH° is the heat of solution at infinite dilution,

equal to A//soln (m) — <I>z,(m). AHn is the heat of neutralization at infinite dilution. In a reaction between a strong acid and a strong base at finite and equal concentrations, given

by HX-nH2 0 + MOH*nH2 0 = MX-(2n + 1)H2 0, Atf°

is equal to \Hn~ [

<I)z.MX'(2n + 1)H20 — <3>/,MOHnH2 0-0LHX-nH2 0].

AHi is the heat of ionization or dissociation of a weak acid or base into its ionic species, such as, HA + H2 0 = H3 0+ + A- and RNH2 + H2 0 = RNH+

+ OH-.

Ki refers to the equilibrium constant of the above

type reactions, with Ka and Kb referring specifically

to the equilibrium constants of the acid and base

reactions, respectively.

The properties were calculated, wherever possible, over the entire range from infinite dilution to approximate saturation or to a 1 : 1 mole ratio. Use

was made of Seidell’s and Linke’s compilations

[615, 616, 617] to obtain the saturation concentrations. Values for <!>*, and <I>c were estimated for

some electrolytes when there was enough information available on the other members of the

family.

1
II. Units of Energy and Constants

The unit of energy used is the thermochemical

calorie, defined by the relation 1 thermochemical

calorie = 4.1840 J. The 1961 atomic weights are used [16]. The values for the specific heat of water

are those recommended by the International Committee of Weights and Measures as given by Stim- son [17]. The conversion factors for correction

to the thermochemical calorie are taken from [18]

and [618]. Unless otherwise mentioned the specific heats of the pure solutes used to correct A//soln to 25 °C have been obtained from Kelley [19] and

Kelley and King [20]. The values of the limiting

slopes appearing in the Debye-Huckel theory of

strong electrolytes are taken from Harned and

Owen [9]. The emf data, on the whole, were used

as summarized by Harned and Owen. The heats of

vaporization of H20 used in the calculations on the

dissociation pressures of the hydrates were obtained

from Osborne, Stimson, and Ginnings [649]. Whenever sufficient data appeared in the original article,

the results were completely recalculated, making appropriate corrections for the specific heat of water,

atomic weights, calorie used, etc. When the details given were insufficient to make exact corrections, the experimental results were corrected on

the basis of reasonable estimates of the quantities

employed by the authors.

III. Uncertainties

The uncertainties assigned to the various values

have been based on many factors — the experimental

technique used, the' details given, the number of

measurements, the standard deviation, the magnitude of the corrections to 25 °C (and to infinite di- lution, for A//£), the inherent error in the methods

used, the reliability of previous work of the in- vestigators, etc. A strictly mathematical evaluation can therefore not be made. The personal

appraisal is an important part of the overall evaluation. For example, the standard deviation of Wiist

and Lange’s [21] work on KC1 is ±1 cal, but the

assigned uncertainty is larger; the value selected

as the “best” value is 40 cal lower than theirs. As

in the above case, the standard deviation and also

the assigned uncertainty can be misleading. In

other cases it is not possible to assign an uncertainty

because of the lack of information.

IV. The Apparent Molal Heat Capacity

A great many investigators have measured the

specific heats of aqueous electrolyte solutions al- though only a few have done so with sufficient precision to give reliable results for the apparent molal

heat capacity of the solute. Harned and Owen [8]

have pointed out the difficulty in obtaining satisfactory results in very dilute solutions. They show,

for example, that at a concentration of 0.01 molal an error of 0.01 percent in the specific heat measure- ments results in an error of about 10 cal/deg mole

in the apparent molal heat capacity of the solute,

whereas an error of 1 percent in the determination

of the concentration results in an error of only 0.5

cal/deg mole. For this reason a great deal of reli- ance has been placed on the Debye-Huckel theory

in the very dilute region.

The measurements of specific heat were con- verted to 4>c. The values for <l>c were plotted

against m1/2 on large scale graphs. The first three

systems treated were NaCl, HC1, and NaOH, at the

various experimental temperatures. This was

done to determine the temperature coefficients,

which in general were applied to other systems

when necessary to correct to 25 °C. In general

the curve was drawn down to m1/2 = 0.4 following

the data available as closely as possible. The

curve was continued so that as m1/2 — 0, the slope,

d^cldm112

, approached the limiting value (6.13 at 25 °C).

Preliminary values for <I>£ at 25 °C for the hydroxides, chlorides, bromides, iodides, and nitrates

of H, Li, Na, and K were obtained. It was assumed

that the heat capacities of the individual ionic species are additive at infinite dilution. Equations

of the following sort were set up:

^(H+)+<D°(Cl-) = Oc°(HCl)

<D£(Na+

) + 4>£(C1-) = <D£(NaCl)

0>^(K+) + <D°(Cl-)=<I>c

o (KCl)

d>°(H+

) + 4>°(Br-) = <Dc°(HBr)

<D£(Na+

) + $c(Br-) = <D°(NaBr)

$°(K^) + <D°(Br-) = (D°(KBr)

<D°(H+

) + $°(N03 -) = <£°(HN03) <D^Na+

) + <I>^N03 -) = <Dc°(NaN03 ) <D£(K+>+ <D£(N03-) = <I)^KN03 ).

<I>c(H +

) was set equal to 0. The values of <!>£ for each electrolyte were weighted proportionally

to their estimated reliability. By cross substituting

values, values for the individual ions were obtained.

The various values for each ion were weighted,

depending on the source, and averaged. The

<D£ values of the electrolytes were then adjusted to be self-consistent.

The values obtained were checked by the method

of Guggenheim and Prue [22] as adapted by Pitzer

and Brewer [10]. The results agreed well within

the uncertainties. Thus, Pitzer and Brewer’s

values of <!>£ for NaCl ( — 22.1 cal/deg mole) and

KC1 ( — 27.7) compare favorably with —21.5 and — 27.4, respectively, obtained here by the above

simple approach. If their method is used with the

experimental data used here, values of —21.9 and

—27.8 are obtained. The difference between

<l>£(Na+

) and <1>£(K+) in this work is 5.9 as compared

to 5.6; for Cl- and Br~, 1.3 as compared to 1.2. It was therefore felt that there was no appreciable

difference in results due to the method of extrapolation, but rather that it was which data were used

and how the experimental data were treated that

was more important. It was also felt advantageous

2
to treat each system individually. Very few adjustments were found to be necessary to make the

results consistent, not only for <!>£, but also for <1>l, A//°, and AH°N, at 25 °C.

Once the values for the above mentioned ions were determined, they were subtracted from the

<S>°C values obtained later for other compounds to obtain the values for the other ions in table I. The values of <!>£ of HC1, NaOH, and NaCl

(table II) at temperatures other than 25 °C were

not adjusted, since there were insufficient data available on the other systems to give an adequate number

of values of <I>£ for smoothing.

The values of <I>£ for all compounds considered

are given in tables III to IX. Graphic representation of the various families of curves, as well as

a detailed curve for KC1, are given in figures I through VIII. The available data for each compound are summarized in the following section. For each substance are fisted the various investigations, with

the temperature and range of concentrations measured. The investigations given the greatest weight

in the evaluation of <l>c are marked with an asterisk.

The substances are discussed in the order: acids,

ammonium and amine salts, silver salts, and salts

of the alkali metals.

HF

The specific heat has been measured by Baud

[23] (15 °C, m = 11.72), Pranschke and Schwiete

[24]

* (18 °C, m= 34.30 to 5.44), Kolesov, Skuratov,

and Uvarov [25]* (25 °C, m = 2.01 to 0.01), Thorvaldson and Bailey [26]* (19 °C, m = 46.37 to 0.28),

Roth and Chall [27] (50 °C, and between 20 and

50 °C, m = 13.26), Roth, Pahlke, Bertram, and

Borger [28]* (20 °C, m— 2.22 to 0.11), and Mulert

[29] (17-18 °C, 7/1= 17.5 to 2.63).

HC1 The specific heat has been measured by Thomsen

[30]

* (18 °C, 777 = 5.55 to 0.56), Marignac [31, 32]*

(22 °C, 771 = 2.22 to 0.56), Richards and Rowe [33,

34] (18 °C, 777 = 0.28), [35, 36] (18 °C, 777 = 0.56 and

0.28), and [37]* (18 °C, 777 = 5.55 and 2.77), Richards,

Rowe, and Burgess [38] (20 °C, 777 = 6.30 and 2.78),

Roth and Chall [27] (50 °C, and between 22.5 and

50 °C, 777 = 2.25), Ackermann [39]* (10, 20, 40 to 120 °C, 777 = 2.00 to 0.50), Vrevskii and Kaigorodov

[40, 41]* (3.3, 20.5, 40.4, and 60.5 °C, 777 = 16.60 to

0.17), Tucker [42] (10 °C, 777 =12.67 to 2.57), Richards, Mair, and Hall [43]* (16, 18, and 20 °C, 777 =2.22

to 0.56), Thorvaldson, Brown, and Peaker [44]* (18

and 19 °C, 777 = 2.78), Drucker [45]* (18 °C, 777 = 2.65

and 1.25), Radulescu and Jula [46]* (15 °C, m = 2.08),

Wicke, Eigen, and Ackermann [47]* (20, 40, 60 to 130 °C, 777 = 1.91 to 0.59), Randall and Ramage [48]*

(25 °C, 777= 1.05 to 0.08), Gucker and Schminke

[49]* (25 °C, 777 = 2.01 to 0.01), and Sturtevant [50]*

(25 °C, 777 = 0.87 to 0.02). The J2 values obtained

here^ agree well with Bates and Bower’s [51] values

of J2 from emf measurements below 777 = 0.1 and

Harned and Owen’s [9] tabulation of J2 obtained

from the extended Debye-Hiickel equation. For

0.1 ^ 777 4.0 the J2 values are below and within 2

cal/deg mole of the values tabulated by Harned and

Owen from Harned and Ehlers’ emf data. As

/77 —> 4.0 the difference becomes 1 cal/deg mole.

Other emf measurements since 1955 have been

reported by Hayes and Lietzke [52] (25 to 50 °C,

777 = 0.1 to 0.001), Greeley [53] (25 to 200 °C, 777= 1.0 to 0.005), Covington and Prue [54] (25 °C, 777 = 0.07

to 0.005) and [55] (25 °C, 777 = 0.1 to 0.005), Oiwa [56]

(25 °C, 777 = 0.1 to 0.001), Taylor and Smith [57]

(10 to 45 °C, 777= 1.5 to 0.9) and Aston and Gittler

[58] (25 °C, 777 = 4.0 to 1.2).

HCIO4

The specific heat has been measured by Berthelot

[59, 60] (between 15 and 40 °C, 777 = 9.0 to 0.05),

and Richards and Rowe [36] (18 °C, 777 = 0.56).

The data were not considered reliable for a 4>c curve. HBr

The specific heat has been measured by Tolloczko and Meyer [61] (13.25 °C, 777 = 4.1), Richards

and Rowe [35, 36]* (18 °C, 777 = 0.56), Roozeboom

[62]* (between 12 and 30 °C, 777 = 30. 17 to 0.28), and

Johnson, Gilliland, and Prosen [63]* (25 °C, m

= 11 . 10). J2 values were compared with Harned and Owen’s

[9], and Biermann and Yamasaki’s [64] emf data.

The agreement is good.

HI

The specific heat has been measured by Richards

and Rowe [36]* (18 °C, 777 = 0.56), and Johnson,

Gilliland, and Prosen [63]* (25 °C, 777 = 7.60).

HIO3

The specific heat has been measured by Randall

and Taylor [65]* (25 °C, 777 = 3.60 to 0.07).

HNO3

The specific heat has been measured by Thomsen [30]* (18 °C, 777 = 5.55 to 0.23), Marignac [66]*

(between 21 and 52 °C, 777 = 1.10 to 0.56), Mishchenko and Ponomareva [67]* (21 °C, extremely

concentrated solutions to 1.24), Forsythe and

Giauque [68]* (25 °C, 777 = 35.55 and 18.50), Roth

[69]* (20 °C, 777 = 0.27 to 0.03), Drucker [45]* (18 °C,

777 = 2.41 to 1.06), Richards and Rowe [36] (18 °C,

777 = 0.56) and [70]* (18 °C, m— 5.55 to 0.14), Lloyd

and Wyatt [71] (0 °C, extremely concentrated solutions), Bump et al. [72] (0 to 26.7 °C, extremely con- centrated solutions), and Booman, Elverum, and

Mason [73] (0 °C, extremely concentrated solutions).

ch2 o2 The specific heat of aqueous formic acid has

been measured by Bury and Davies [74]* (15 °C,

777= 10.06 to 1.33), Ackermann and Schreiner [75]*

(0, 10, 20, 30 to 130 °C, 777 = 2.84 to 0.49), and Glagoleva and Cherbov [76]* (25, 60, and 80 °C, 100%

tO 777 = 4.185).

740-560 0 - 65-2

3
The specific heat of CH2 02(1) has been measured by von Reis [77], Radulescu and Jula [46],

Berthelot and Ogier [78], Pettersson [79], Glagoleva

and Cherbov [76], Gibson, Latimer, and Parks [80]*,

and Stout and Fisher [81]*.

c2 h4o2 The specific heat of aqueous acetic acid has been

measured by Marignac [32, 66]* (between 21 and

52 °C, m = 22.2 to 2.22), Neiman [82, 83]* (23.9,

42.0, 59.5, and 80.5 °C, 100% to 777 = 0.96), Richards

and Gucker [84]* (16, 18, and 20 °C, 777 = 2.22), von

Reis [85]* (18 °C, m— 2.22), Bury and Davies [74]*

(15 °C, m = 8.66 to 0.91), and Ackermann and

Schreiner [75]* (10, 20, 30 to 130 °C, m = 3.00 to

0.50).

Richards and Gucker [84]* calculated the specific heat (18 °C, 777 = 1.11 to 0.07) from A//diln and

the value of the specific heat at m — 2.22.

The specific heat of C2 H402(1) has been measured by Radulescu and Jula [46]*, von Reis [77],

Parks and Kelley [86]*, Swietoslawski and Zielenkiewicz [87], Neiman [82, 83]*, Marignac [32], and

Berthelot [88].

C3 H6O2 The specific heat of aqueous propionic acid has

been measured by Bury and Davies [74]* (15 °C,

777 = 5.84 to 777 = 0.49) and Ackermann and Schreiner

[75]* (0, 10, 20, 30 to 130 °C, m = 2.00 to 0.50).

nh3 The specific heat has been measured by Riihlemann [89] (between 22 and 99 °C, 7/1=1.35), Vrevskil and Kalgorodov [40, 41]* (2.4, 20.6, 41, and

60.9 °C, m — 28.01 to 0.84), and Hildenbrand and

Giauque [90]* (25 °C, m — 55.51, and —73 to —18

°C, more concentrated solutions).

nh4f

The specific heat has been measured by Labowitz and Westrum [91]* (25 °C, 7/7 = 0.50 to 0.005).

NH4C1

The specific heat has been measured by Thomsen

[30]* (18 °C, m = 7.40 to 0.28), Marignac [32]* (between 20 and 52 °C, m = 4.44 to 0.56), Drucker [45]*

(18 °C, m = 4.73 to 1.10), Mishchenko and Ponomareva [67, 92]* (25 °C, m — 7.03 to 0.31), D’Ans

and Tollert [93]* (21, 41, 70, and 86 °C, m = 3.28

and 1.67), Winkelmann [94]* (15 to 28.6 °C, 777 = 6.23

to 0.58), Faasch [95]* (18 °C, m = 3.96 to 0.47), and

Urban [96]* (20, 25, 30, 35, and 40 °C, //i = 2.00).

The value for <I>£NH4 + was obtained by subtracting <D£C1- from <L£NH4C1.

NH4 Br

The specific heat has been measured by Thomsen

[30] (19 °C, 7/1 = 0.28) and Faasch [95] (18 °C, m =

4.02 to 0.50). The <I>c fine, however, was estimated.

<J>£NH4Br was obtained from T>^NH4 + and <l>£Br~

NH4 I Thomsen [30] measured the specific heat (18 °C,

m = 0.28). The <f>c curve was essentially estimated,

using <Lf NH4 I from the ions.

nh4no3 The specific heat has been measured by Thomsen

[30]* (18 °C, 77/=11.10 to 0. 56), Marignac [32, 66]*

(between 20 and 50 °C, m= 11.10 to 0.56), Tollinger

[97]* (23.5 °C, 7/1 = 0.56) Zwicky [98] (20 °C,

7n = 28.61 to 1.39), Lerner-Steinberg [99]* (21.6 °C,

7/7 = 0.60 and 0.44), Chauvenet [100] (15 °C, m = 1.33),

Drucker [45]* (20 °C, 777 = 4.99 and 1.05), Rutskov

[101, 102]* (25, 50, and 75 °C, 7/7=18.50 to 0.56),

Winkelmann [94]* (16 to 38 °C, 777 = 8.33 to 0.39),

Cohen, Helderman, and Moesveld [103, 104]

(32.3 °C, 777 = 28.41 to 1.39), and Gucker, Ayres, and

Rubin [105, 106]* (25 °C, 7/7 = 24.00 to 0.10).

CH3NH3C1

The specific heat has been measured by Whitlow

and Felsing [107]* (25 °C, 777 = 0.96 to 0.09). <l>c is tabulated only in the range from 777 = 1.1 1 to 0.09

since the data available are not considered reliable

for extrapolation to infinite dilution. A rough

extrapolation leads to a value for <!>£ of —1 cal/deg

mole.

(CH3)2 NH2 C1

The specific heat has been measured by Whitlow

and Felsing [107]* (25 °C, 7/7 = 0.98 to 0.11). <f> c is tabulated only in the range from 777 = 1.11 to 0.09

since the data available are not considered reliable

for extrapolation to infinite dilution. A rough

extrapolation leads to a value for <t>£ of +2 cal/deg

mole.

(CH3 ) 3NHC1

The specific heat has been measured by Whitlow

and Felsing [107]* (25 °C, 777= 1.0 to 0.09). <I>c is tabulated only in the range from 777 = 1.1 1 to 0.09

since the data available are not considered reliable

for extrapolation to infinite dilution. A rough

extrapolation leads to a value for of +4 cal/deg

-mole.

AgF

The specific heat has been measured by JahnHeld and Jellinek [110]* (25 °C, 777= 14 to 1). Values for <f>c are given at infinite dilution and

above 7/7 = 2. AgN03 The specific heat has been measured by Marignac

[66]* (between 25 and 52 °C, 7/7 = 2.22 to 0.56)

and Kapustinskil, Yakushevskil, and Drakin

[111]* (25 °C, 777= 1.80 to 0.28). Roth [69]* gives an

equation for the range 7/7 = 0.22 to 0.08 at 18.5 °C.

LiOH

The specific heat has been measured by Richards

and Rowe [70]* (18 °C, 7/7 = 2.22), and [36] (18 °C,

777 = 0.56), and Gucker and Schminke [112]* (25 °C,

7/7 = 2.27 to 0.04).

4
Richards and Rowe [70]* calculated the specific

heat (18 °C, /re =1.11 to 0.14) from AHdnn at 16 and

20 °C and the specific heat at /re = 2.22.

The <J>C curve was based primarily upon Gucker

and Schminke’s measurements.

LiCl

The specific heat has been measured by Tucker

[42] (14 to 22 °C, m = 16.34 to 2.52), Chernyak [113]

(25 °C, m = 1.0), Bennewitz and Kratz [114]* (20 °C,

m= 1.0 to 0.05), White [115]* (25 °C, m = 0.05),

Jauch [116] (18 °C, m = 4.06 to 0.50) Hess [117]* (25

°C, /re = 0.15), Drucker [45]* (18 °C, m = 9.8 to 1.3),

Gucker and Schminke [49]* (25 °C, m = 2.46 to 0.04),

Richards and Rowe [70]* (18 °C, m = 2.22), and

Lange and Diirr [118]* (25 to 28 °C, m— 19.89 to

0.56).

Richards and Rowe [70]* calculated the specific

heat (18 °C, /re = 1.11 to 0.14) from Ai/diln and the

specific heat at m = 2.22.

The <DC lines of Gucker and Schminke, and

Lange and Diirr are parallel to one another. There seems to be a systematic error in the latter’s work.

The final <l>c line is based primarily on Gucker and

Schminke’s work.

LiBr

The specific heat has been measured by Jauch

[116]* (18 °C, /n = 4.45 to 0.51), Lange and Schwartz

[119]* (26.5 °C, m = 17.92 to 0.04), and Eigen and

Wicke [120]* (10, 20, 40, 60 to 120 °C, /re = 0.56,

0.91, and 1.32).

Here as in LiCl, the <I>c fines of Eigen and Wicke

and Lange and Schwartz are parallel. Eigen and

Wicke’s fine was essentially used, with Lange and

Schwartz’s 4>c values lowered by a constant amount

to coincide with Eigen and Wicke’s.

Lil

The specific heat has been measured by Jauch

[116]* (18 °C, m = 3.17 to 0.51).

LiNOa

The specific heat has been measured by Chauvenet [100] (15 °C, /re = 2), Drucker [45]* (18 °C,

/re =1.89 to 0.91), and Richards and Rowe [70]*

(18 °C, /re = 2.22). The latter also used A//dUn at 16

and 20 °C to calculate the specific heat from m = 1.11

to 0.14 at 18 °C.

NaOH

The specific heat has been measured by Thomsen

[30]* (19 °C, m = 7.40 to 0.28), Bertetti and McCabe

[121]* (3.12 to 60 °C, m = 22.81 to 1.06), Richards

and Rowe [36]* (18.1

dC, m = 0.56 and 0.28), Ackermann [39, 122]* (10, 20, 40, 60 to 130 °C, m = 2.00 to

0.50), Richards and Gucker [84]* (16, 18, and 20 °C,

m = 2.22), Sturtevant [50]* (25 °C, m = 0.087 to 0.006), Tucker [42] (16 to 21 °C, m = 22.54 to 4.92),

Richards and Hall [123]* (18 °C, m = 2.22 to 0.56),

Roth, Wirths, and Berendt [124] (19.8 °C, m — 10.11),

Wilson and McCabe [125]* (29.8 to 122 °C, /re = 26.76

to 25.20), and Gucker and Schminke [112]* (25 °C,

m = 2.55 to 0.04),

The values of J2 obtained here agree well with

those given by Harned and Owen [9] and Akerlof

and Kegeles [126] below m = 2. NaCl

The specific heat has been measured by Thomsen

[30] (19 °C, m= 5.55 to 0.28), Marignac [32] (18 °C

and between 22 and 52 °C, m = 2.22 to 0.56),

Stakhanova and Vasilev [127]* (25 °C, /re = 4.37 to 0.20), Biron [128] (19 °C, m = 0.28 to 0.07), Blaszkowska [129]* (21.4 °C, /re = 2.22 to 0.28), Zdanovskii

[130]

* (25 °C, m — 2.33), Zdanovskii and Suslina

[131]

* (25 °C, m = 1.89), Zdanovskii and Matsenok

[132]

* (25 °C, /re = 6. 11 to 1.75), Eigen and Wicke

[120]* (10, 20, 40 to 130 °C, m = 1.12 to 0.41),

D’Ans and Tollert [93] (21 and 41 °C, m — 5.75 to

1.66), Drucker [45]* (20 °C, m = 4.36 to 1.02), Chipman, Johnson, and Maass [133]* (18.8 and 25.4 °C,

/re = 2.54 to 0.43), Nikolaev, Kogan, and Ogorodnikov

[134]* (25 °C, /re = 6. 15 to 0.34), Winkelmann [94]

(17 to 46 °C, m = 5.48 to 0.53), Leitner [135] (25.7

to 95.7 °C, m = 5.97), Hess [117]* (25 °C, m = 0.15

to 0.003), White [136]* (35 to 45 °C, m = 0.20 to 0.01), Hess and Gramkee [137]* (15, 25, 35, 45 °C,

m — 1.03 to 0.01), Voskresenskaya and Yankovskaya

[138] (50 °C, m = 57.6 to 3.45), Lipsett, Johnson, and

Maass [139]* (25 °C, m =6.01 to 0.17), Bousefield

and Bousefield [140]* (7, 20, and 33 °C, /re = 5.70 to 0.25), Rutskov [101, 102]* (25, 50, and 75 °C,

m = 5.55 to 0.20), Ackermann [39]* (10, 20, 40, 60

to 130 °C, m — 2.00 to 0.50), Randall and Ramage

[48]* (25 °C, m =1.90 to 0.07), Sandonnini and

Gerosa [141] (18.5 °C, ire =1.12 to 0.20), Person

[142] (0 to 13 °C, m = 9.05 to 1.88), Randall and

Bisson [143]* (25 °C, m =6.20 and 4.04), Randall

and Rossini [144]* (25 °C, m — 2.30 to 0.04), and

Richards and Gucker [84]* (18 °C, m = 2.22).

The J2 values were checked with those obtained

from emf data as given by Harned and Owen [9]. The agreement is excellent below m— 1 and within

3 cal/deg mole between m— 1 and 4. NaClOa

The specific heat has been measured by Colomina

and Nicolas [145]* (24 °C, m =15.39 to 0.20) and

Ferrer [146]* (25 °C, m= 3.11 to 0.19).

NaC104 The specific heat has been measured by Colomina

and Nicolas [145]* (24.5 °C, /re =12.22 to 0.13), and

Ferrer [146]* (25 °C, m = 2.59 to 0.24).

The values of <LC chosen were based on Ferrer’s

data up to m = 2.6 and above that on Colomina’s.

NaBr

The specific heat of aqueous NaBr has been

measured by Marignac [32, 66]* (between 20 and

52 °C, m = 2.22 to 0.56), Chipman, Johnson, and

Maass [133] (25.4 and 18.8 °C, m = 1.88 to 0.24),

Bender and Kaiser [147]* (25 and 30 °C, m = 8.37

to 0.97), Rossini [148]* (25 °C, m = 0.43 to 0.08),

and Randall and Rossini [144]* (25 °C, smoothed

values from m= 1.00 to 0.01).

5
Below m = 2.0 the values obtained here for J2 were below but within 3 cal/deg mole of the emf

values listed in Harned and Owen [9]. NaBrOa

The specific heat has been measured by Ferrer

[146]* (25 °C, m = 2.34 to 0.21).

Nal

The specific heat has been measured by Thomsen

[30]* (18 °C, m = 0.28), Marignac [32, 66]* (between

20 and 51 °C, m = 2.22 to 0.56), Rossini [148]*

(25 °C, m = 0.85 to 0.9), and Randall and Rossini

[144]* (25 °C, smoothed values from m— 1.00 to

0.01).

NaN02 The specific heat has been measured by Ferrer

[146]* (25 °C, m = 2.25 to 0.10) and Perreu [149] (15

°C, m — 11.87 to 1.45).

NaNOs

The specific heat has been measured by Thomsen

[30]* (18 °C, wi = 5.55 to 0.28), Marignac [66]* (20.5

°C and between 22 and 52 °C, m = 2.22 to 0.56), Biron

[128] (19 °C, m = 0.28 to 0.03), Person [142] (0 to 20

°C, m = l.l to 0.59), Magie [150] (room temperature,

w =1.11 to 0.19), D’Ans and Tollert [93]* (21 °C,

ra = 5.0), Winkelmann [94, 151] (2 to 60 °C, m = 2.35

to 0.37), Gerlach [152] (between 20 and 95 °C,

m= 10.2), Richards and Gucker [84]* (18 °C,

m = 2.22), Zdanovskil [130]* (25 °C, m = 2.58), Rossini [148]* (25 °C, m = 0.85 to 0.08), Randall and

Rossini [144]* (25 °C, smoothed values at m= 1.00 to

0.01), Richards and Rowe [70]* (18 °C, m = 2.22),

Drucker [45]* (18 °C, m = 4.59 to 1.03), and Chauvenet [100] (15 °C, m = 2.13).

Richards and Rowe [70]* calculated the specific

heat (18 °C, /n. = 1.11 to 0.14) from the dilution data

at 16 and 20 °C and the specific heat at m — 2.22.

NaCH02 The specific heat of aqueous sodium formate has

been measured by Ackermann and Schreiner [75]*

flO, 20, 30 to 120 °C, m = 2.85 to 0.50).

NaC2 H302 The specific heat of aqueous sodium acetate has

been measured by Thomsen [30]* (17 °C, m = 2.78 to 0.28), Marignac [32, 66]* (22.5 °C, and between 19

and 52 °C, m = 2.22 to 0.56), Richards and Gucker

[84]* (16, 18, and 20 °C, m = 2.22), Perreu [153]* (19

°C, m = 4.78 to 1.36), Bindel [154] (21 °C, m — 5.55 to LIT), Ferrer [146]* (25 °C, m = 2.79 to 0.23), KapustinskiT and Stakhanova [155]* (25 °C, m— 17.13 to

3.14), Ackermann and Schreiner [75]* (10, 20, 30 to 120 °C, m = 2.53 to 0.60). Gnesotto and Fabris

[156] measured the specific heat of the liquid trihydrate at 0 to 100 °C.

Richards and Gucker [157]* calculated the

specific heat (m=1.09 to 0.03) from dilution data

and the specific heat at ra = 2.22, obtained in [84].

NaC3H5 02 The specific heat of aqueous sodium propionate

has been measured by Ackermann and Schreiner

[75]* (10, 20, 30 to 120 °C, m = 2.24 to 0.50).

KOH

The specific heat has been measured by Thomsen

[30]* (18 °C, m= 1.85 to 0.28), Jaquerod [158] (18 °C,

m = 4.92 to 0.95), Gawlik [159]* (20 °C, m = 0.33 to 0.04), Voskresenskaya [160]* (20 °C, m = 4.24),

Richards and Hall [123]* (18 °C, m = 0.56), Gucker

and Schminke [49]* (25 °C, m = 2.59 to 0.04),

Richards and Rowe [36]* (18 °C, m = 0.56) and [70]*

(18 °C, m — 13.38 and 5.55), Sabatier [161] (temperature uncertain, m— 13.37).

Richards and Rowe [70]* calculated the specific

heat (18 °C, m — 2.22 to 0.14) from the dilution data

and specific heats of the more concentrated

solutions.

The agreement of the calculated A values with

those given by Harned and Owen [9] for the emf

values is excellent.

KC1

The specific heat has been measured by Thomsen

[30]* (18 to 20 °C, /n = 3.7 to 0.28), Marignac [32,

66]* (19.5 °C and between 20 and 51 °C, /rr = 1.11 to 0.56), Andrews [162] (18 °C, m = 0.25), Stakhanova and Vasilev [127]* (25 °C, m = 4.60 to 0.20),

Voskresenskaya and Rutskov [163]* (25 °C,

m = 1.40), Biron [128] (19 °C, m = 0.28 to 0.03),

Winkelmann [94] (0 to 55 °C, /n = 5.59 to 0.42), and

[151] (20 °C, m = 0.71), Chipman, Johnson, and

Maass [133]* (18.8 and 25.4 °C, m = 2.48 to 0.33),

Magie [150] (room temperature, to = 1.11 to 0.14),

Sandonnini and Gerosa [141] (18.5 °C, to = 0.75 to 0.17), Jaquerod [158] (18 °C, to = 3.8 to 0.95), Cobb

and Gilbert [164]* (25 °C, to = 1.00 and 0.50),

D’Ans and Tollert [93]* (21 and 41 °C, to = 4.40 to

1.7), Nikolaev, Kogan, and Ogorodnikov [134]*

(25 °C, to = 4.80 to 0.07), Zdanovskii [130]* (25 °C,

to = 2.56), Rutskov [101, 102]* (25 °C, to = 4.63 to 0.10), Popov, Bundel, and Choller [165]* (20 °C,

m — 0.56 to 0.14), Popov, Khomyakov, Feodos’ev,

and Schirokich [166]* (same data as [165]), Urban

[96]* (10 to 40 °C, to= 2.00 to 0.10), Ferrer [146]*

(25 °C, to = 2.98 to 0.05), Hess and Gramkee [137]*

(15, 25, 35, 45 °C, to =1.03 to 0.01), Clews [167]*

(15.6 to 43.2 °C, to = 2.50 to 0.10), Gucker [168]*

(20 °C, to = 2.22), Kapustinskii, Yakushevskii,

and Drakin [111]* (25 °C, to = 1.71 to 0.52), Varasova,

Mishchenko, and Frost [169]* (25 °C, to = 4.85 and

2.73), Randall and Bisson [143] (25 °C, to = 4.85

and 2.73), Bousefield and Bousefield [140]* (20

and 33 °C, m = 3.40 to 0.25), Randall and Rossini

[144]* (25 °C, m = 2.50 to 0.05), Rossini [148]*

(25 °C, m = 2.25 to 0.04), Cohen and Moesveld

[170]* (19 °C, m = 3.39 and 1.03), Parshikov [171]*

(25 °C, m = 0.41), and Richards and Rowe [70]*

(18°C,m = 2.22).

Richards and Rowe [70]* calculated the specific

heat (18 °C, m=l.ll to 0.14) from the directly

determined specific heat at m — 2.22 and their

dilution data. The AHsoln and A//diln experiments

of Wiist and Lange [21]* were sufficiently detailed

6
to permit the computation of the heat capacity of

the solutions. The A//soi n measurements of KC1

at various temperatures were also used to compute

0>c at the mean temperature.

The calculated A values were compared with

those obtained from the emf measurements as given by Harned and Owen [9]. The agreement was good, within 1 cal/deg mole below m = 2. KBr

The specific heat has been measured by Thomsen

[30]* (18 °C, m — 0.28), Marignac [32, 66]* (between

20 and 51 °C, 777 = 2.22 to 0.56), Popov, Bundel,

and Choller [165]* (20 °C, 777 = 0.19), Bender and

Kaiser [147]* (25 and 35 °C, 777 = 5.52 to 1.00),

Rossini [148]* (25 °C, m= 0.97 to 0.04), Randall and

Rossini [144]* (25 °C, smoothed values from m — 1.00

to 0.01), Chipman, Johnson, and Maass [133]*

(25.4 and 18.4 °C, 777= 1.57 to 0.21), Urban [96]*

(10, 15, 20, 25, 30, 35, and 40 °C, m = 2.00), Popov,

Skuratov, and Strel’tsova [172]* (20.2 °C, m = 0.32).

KI

The specific heat has been measured by Thomsen

[30]* (18 °C, 777 = 0.28), Marignac [32] (between 20

and 51 °C, m = 2.22 to 0.56), Drucker [45]* (18 °C,

m — 3.24 to 0.68), Popov, Skuratov, and Strel’tsova

[172]* (20.2 °C, m= 1.63), Rossini [148]* (25 °C,

771 = 0.85 to 0.04), and Randall and Rossini [144]

(25 °C, smoothed values from m— 1.00 to 0.01).

kio3 The specific heat has been measured by Randall

and Taylor [65]* (25 °C, m — 0.38 to 0.04).

kno3 The specific heat has been measured by Thomsen

[30]* (18 °C, 777 = 2.22 to 0.23), Marignac [32, 66]*

(20.5 °C and between 22 and 52 °C, m = 2.22 to

0.56), Person [142] (0.6 to 20.6 °C, 777 = 2.00 to 0.50),

Drucker [45]* (19 °C, 777 = 2.18 and 1.05), Voskresenskaya [160]* (30 °C, 777 = 2.10), Rutskov [101,

102]* (25, 50, and 75 °C, 777 = 0.50 to 6.94), Zdanovskii [130]* (25 °C, 777 = 3.12), Magie [150] (room

temperature, 777 = 2.22 to 0.14), Biron [128] (19 °C,

777 = 0.28 and 0.14), D’Ans and Tollert [93] (41 °C,

777 = 2.78), Winkelmann [94, 151] (4 to 60 °C, m = 2.44

to 0.30), Chauvenet [100] (15 °C, 777 = 2.18), Richards

and Gucker [84]* (18 °C, 777 = 2.22), Andrews [162]

(16.6 °C, 777 = 0.26), Gucker [168]* (20, 50, and 80 °C,

777 = 2.22), Richards and Rowe [70]* (18 °C, m = 2.22),

Rossini [148]* (25 °C, m= 1.05 to 0.05), Randall and

Rossini [144]* (25 °C, smoothed values at 777 = 1.00 to 0. 01). Lange and Monheim [173]* calculated the specific

heat at 18.75 °C from the solution and dilution

experiments at 12.5 and 25.0 °C at 777 = 0.146 to 0.0004. Richards and Rowe [70]* calculated the

specific heat (18 °C, 777 = 1.11 to 0.14) from dilution

data and the measured specific heat at 777 = 2.22.

KCNS

Urban [96]* has measured the specific heat (10,

15, 20, 25, 30, 35, and 40 °C, 777 = 2.63 to 0.50).

kc2 h3o2 The specific heat of aqueous potassium acetate

has been measured by Marignac [32, 66]* (between

20 and 51 °C, 777 = 11.11 to 2.22), Drucker [45]*

(18.6 °C, 777 = 5.62 to 1.05), Urban [96]* (10, 15, 20,

25, 30, 35, and 40 °C, 777 = 2.36 to 0.25), and Andrews

[162] (18 °C, 777 = 0.25).

KMnCL

The specific heat has been measured by Perreu

[174]* (19 °C, 777 = 0.40 to 0.063) and Kapustinskil

and Klokman [175]* (25 °C, 777 = 0.32 to 0.03).

KClOa

The specific heat has been measured by Bindel

[154] (20 °C, 777 = 2.78 to 0.56). The data were not

considered reliable for a line.

Cs and Rb Compounds

The scarcity of concordant information on the Cs

compounds makes the selection of <I>£Cs +

difficult. The selection depends on whether the data of

Richards and Rowe [70] at 18 °C on CsCl or CsN03 , or the data of Kapustinskil and coworkers [176, 177,

178, 179] on Csl at 25 °C are utilized. It was felt that the more recent measurements on Csl are the

more reliable. This choice necessitated estimating

the other <I>c lines, which were drawn to be consistent with the Csl and the K compounds.

Since there was no reliable information available on the Rb compounds to determine <I>£Rb +

, the

value was estimated on the basis of values of <I>£ of Cs+

, K+, and Na+ . The data available for each compound follow:

Rbl

Jauch [116] has measured the specific heat (18 °C,

777 = 3.14 to 0.05).

RbNOa

Chauvenet [100] has measured the specific heat

(15 °C, 777 = 1.45).

CsCl

The specific heat has been measured by Bennewitz and Kratz [114]* (20 °C, 777 = 0.41 to 0.01) and

Richards and Rowe [70]* (18 °C. 777 = 1.11 to 0.14).

Csl

The specific heat has been measured by Kapustinskil, Yakushevskil, and Drakin [176]* (25 °C,

777 = 0.73 to 0.15), and Kapustinskil, Lipilina, and

Samoilov [177, 178]* (25 °C, 777 = 1.06 to 0.22).

Kapustinskil [179]* reported the same values.

CsN03 The specific heat has been measured by Chauvenet [100] (15 °C, 777 = 0.61) and Richards and Rowe

[70]* (18 °C, 777 = 0.93 to 0.14).

7
Figure I. The apparent molal heat capacity, Oc, of KC1 in cal/deg mole, at 25 °C as a function of m4 . The vertical line indicates the assigned uncertainty of the determination. The series of the determinations are:

(1) Ferrer [146] (8) Nikolaev, Kogan, and Ogorodnikov

(2) Rossini [148] [134]

(3) Randall and Bisson [143] (9) Cobb and Gilbert [164]

(4) Kapustinskii.Yakushevskii, and Drakin (10) Voskresenskaya and Rutskov [163]

[111] (11) Zdanovskii [130]

(5) Hess and Gramkee [137] (12) Clews [167]

(6) Urban [96] (13) D’Ans and Tollert [93]

(7) Varasova, Mischenko, and Frost [169]

Figure II. $c as a function of m4 in aqueous solutions o/HCl,

HBr, HI, HN03 , LiOH, LiCl, LiBr, Lil, and LiN03 at 25 °C.

FIGURE III. <I>c as a function of m4 in aqueous solutions of NH4 C1, NH4Br, NH4 N03 , NaOH, NaCl, NaBr, Nal, NaNO*,

and NaN03 at 25 °C. NH,Br is estimated.

8
Figure IV. 3>c as afunction of in aqueous solutions o/KOH,

KC1, KBr, KI, KN03, KCNS, Rbl, Csl, and CsN03 at 25 °C. CsN03 and Rbl are estimated.

'IriT

Figure V. <I>C as a function of m* in aqueous solutions o/HI03 , NaC103 , NaC104 , NaBr03 , NaN02 , NaN03 , KI03, and KMn04 at 25 °C.

Figure VI. Oc as a function of m* in aqueous solutions o/HCl,

NH4 C1, NaCl, KC1, RbCl, and CsCl at 25 °C. RbCl and CsCl are estimated.

FIGURE VII. Oc as a function of m* in aqueous solutions of Na

formate, Na acetate, Na propionate, and K acetate at 25 °C.

Figure VIII. <tv OS a function of mH in aqueous solutions o/HF,

formic acid, acetic acid, propionic acid, and NH4 OH at 25 °C.

9
V. Heats of Dilution

A great deal of the data from which <t>L is obtained

appears in the literature in the form of measure- ments of AHsoln as a function of concentration.

By taking the difference between two measured

A//soln at concentrations mi and m2 , the A//diln between the two concentrations is obtained. The

A//soln data treated in this way can be combined

with the directly measured A//di i n data.

As in the case of the specific heat measurements,

the original data were corrected as completely as possible to conform with the present best values of

atomic weights, energy units, etc. The more important sets of measurements were completely

recalculated from the experimental data whenever

the necessary information was available. When

necessary, the data were corrected to 25 °C using

the values of <l>c selected earlier.

The method used to obtain the values of <!>/, is the chord-area method developed by Young and

coworkers [180, 181, 182, 183]. (An alternative

method is that of Guggenheim and Prue [184]

which leads to essentially the same results.) The

chords A<f>zVA(ra1/2

) were plotted against m1/2 on

large scale graphs. The extrapolation to infinite

dilution was made using 472 cal/mole3/2 for the

limiting value of d<i>Lldm112

. A smooth curve was

drawn through all the data, giving greater weight to the more reliable data. The d^ijdm112 curves for

NaCl and KC1 resulting from the graphical method

were compared with the curves obtained from

least squares treatments of the same data. The

results agreed well; it was therefore felt unnecessary to apply the least squares treatment to the less

extensive data for the other systems. The re- sultant d<t>L/dm112 curve was integrated to obtain

In areas where was not well defined by

the chord area plot, and long chords were available,

values were obtained directly by using the ex- perimental A//diln and <I>l for the defined area. In

other cases where reliable \Hn data were available,

<1 was obtained directly. All values so obtained were consistent with the $>L values obtained

by the chord' area method. There was very little necessity for adjusting values, lending support to the methods used and to the corrections applied.

A detailed plot of the chord area treatment of

NaCl is shown in^ figure IX. The values of

d<t>L/dm112

, 4>l, and L2 for NaCl are given in table X.

Representative graphs of <I>t for the various families are given in figures X-XIV. The detailed results are tabulated in tables XI-XVI.

The data available for each compound follow:

HF

A//diln has been measured by Petersen [185]

(21.5 °C, one dilution from /n = 0.20 to 0.10), Roth

[186] (20 °C, m = 0.37 to 0.11), Guntz [187] (17 °C,

m— 111.012 to 0.14), Schafer and Kahlenberg

[188]* (25 °C, one dilution from m — 34.43 to 2.82)

and [189]* (25 °C, one dilution from m = 0.33 to 0.03), and Roth, Pahlke, Bertram, and Borger [28]*

(20 °C, m = 24.0 to 0.04).

The values of AHi were obtained from the variation of Ki with temperature for the reactions*

(1) HF = H+ + F- and (2) HF + F- = HF2 , using

the data of Roth [186], Broene and DeVries [1901*.

and Wooster [191]*.

Other information on the ionization of HF can be obtained from the AHN data of Thomsen [30]

(with NaOH), von Steinwehr [192] (unspecified),

Petersen [193] (with LiOH), Arrhenius [194] (with

NaOH), Guntz [187] (with KOH and NH3), Mulert

[29] (with NaOH and KOH), Roth and Becker

[195] (with NaOH), and Berthelot and Guntz [196]

(HC1 with KF).

The greatest weight was given to Wooster’s

data. The selected values at 25 °C are: A//(l) = — 3,000 cal/mole and A//(2) = + 662 cal/mole.

Elmore, Hatfield, Mason, and Jones [197] reviewed

the thermal properties of aqueous HF and, using

Wooster’s Ki s, calculated the percentage of each

ion in solution at various concentrations of HF.

These percentages were used with the above determined A//i’s for reactions (1) and (2) to determine

their contribution to AHsoln and Atfdiln . These

heats were combined with the dilution data to obtain

<&l for the complete range. The values as tabulated are to be used only with the A//° for

complete dissociation into the ions H+ and F

-

. HC1

AHdnn has been measured by Thomsen [30]*

(16.5 °C, m = 21.2 to 1.11), Berthelot [198]* (15 °C,

m = 25.58 to 0.25), Naude [199]* (12 and 18 °C,

m = 1.0 to 0.0001), Tucker [42]* (15 to 20 °C, m = 13.0

to 1.34), Becker and Roth [200]* (20 °C, m = 5.38

to 0.28), Richards, Mair, and Hall [43] (18 °C,

m = 2.22 to 0.07), Richards and Rowe [37]* (18 and

20 °C, m = 5.55 to 0.14), von Steinwehr [192] (16 °C,

m = 4.7 to 0.005), Muller [201] (16, 26, and 38 °C,

m— 1.0 to 0.01), Thorvaldson, Brown, and Peaker

[44]* (20 °C, m = 2.78 to 0.28), Petersen [185]

(21.5 °C, m = 0.56 to 0.19), Richards, Rowe, and

Burgess [38] (25 °C, m = 6.30 to 0.28), Roth [69]*

(20 °C, m=l.ll to 0.02), Vrevskil and Zavaritskil

[202]* (15 °C, m = 15.59 to 1.10), Myers [203]* and

Vanderzee and Myers [204]* (25 °C, m = 4.49 to 0.07), Sacconi, Paoletti, and Ciampolini [205]*

(25 °C, one dilution from m=1.70 to 0.03), Pitzer

[206]* (25 °C, one dilution from m = 1.19 to 0.05),

Sturtevant [50, 207, 208]* (25 °C, m = 3.34 to 0.005).

Ellis [209] has calculated the heat of dilution from

emf measurements (25 °C, m — 4.484 to 0.10).

Li has been measured by Roth and Wienert

[210] (20.7 °C, m = 17.28), Schafer, Wittig, and Jori

[211]

* (25 °C, m=16.9),, and Payn and Perman

[212]

* (20 and 30 °C, m= 16.38 to 1.60).

Bender and Biermann [213]* measured AHs of

HC1 with NaOH (25 °C, /7iHci = 16.39 to 3.01).

Vrevskil and Zavaritskil [202, 214] measured

A//soln as a function of concentration (3.6, 21.5, 42,

and 62.3 °C, m= 16.37 to 0.18).

The chord area plot was used to define the curve; chords were obtained from AHdi \ n and A//soi n

. The $>L curve which was obtained was adjusted in

10
the region from m — \6A to 4.9 to include the 4v

obtained from the neutralization measurements.

The greatest weight below m = 5 was given to Sturtevant’s corrected data, and above to Bender

and Biermann’s. Thomsen’s and Berthelot’s

data were used between tti= 16 and 27. The last

two values are extrapolated ones. The calculated values of L2 agree within 10 cal/

mole through m — 2.56 with those given by Harned

and Owen [9] from emf measurements.

HC104 A//diJn has been measured by Berthelot [59, 215,

216, 220] (19 and 21 °C, tti = 55.5 to 0.28), Krivtsov,

Rosolovskil, and Zinov’ev [217]* (25 °C, extremely

concentrated solutions to 771 = 0.07), Wood [218] (25

°C, one dilution from tti = 0.52 to 0.49), Austin and

Mair [219] (25 °C, one dilution from m — 0.52 to

0.02), and Vanderzee and Swanson [221]* (25 °C,

m= 10.76 to 0.004).

4V was based primarily upon Vanderzee and

Swanson’s measurements. Above m = 1 1, the

results of Krivtsov et al., were used.

HBr

A//diln has been measured by Thomsen [30]*

(19 °C, m = 25.12 to 0.28), Berthelot [198]* (15.5 °C,

m = 27.14 to 0.10), Petersen [185] (21.5 °C, m — 0.56

to 0.28), Roozeboom [62] (0 and 8.2 °C, m = 27.8 to

0.25), and Louguinine and Schukareff [222] (18 °C,

m = 6.49 to dilute solutions).

Biermann and Weber [223]* measured AHN of

HBr with NaOH (25 °C, /nHBr = 16 to 3). Their

results were used in this range to obtain 4V. Thomsen’s data and Berthelot’s data were used above and

below this range and coordinated with the eipf data, as given by Harned and Owen [9], below 777 = 0.4

to complete the 4v curve. HI

Below 777 = 0.56 values of 4v were estimated on

the basis of a comparison of LiCl-LiBr, NaClNaBr-Nal, and HCl-HBr. Above m = 0.56 the

A//diln measurements of Thomsen [30]* (18.5 °C,

m= 19.41 to 0.23) and Berthelot [198]* (14 °C,

m — 18.82 to 0. 16) were used.

Richards and Rowe’s [224]* AHn (15.5 and 17 °C,

^hi = 0.56) with NaOH and KOH were used as corroborating evidence.

HNO3 A//di i n has been measured by Thomsen [30]*

(18.8 °C, extremely concentrated solutions to

777 = 0.28), Berthelot [225] (9.7 and 26 °C, m = 2.72

to 0.69) and [226, 227]* (9.7 °C, extremely concentrated solutions to 0.69), Petersen [185] (21 °C,

777 = 0.67 to 0.17), Richards and Rowe [70]* (20 °C,

m = 5.55 to 0.14), Naude [199]* (18 °C, 777= 1.03 to 0.0003), Becker and Roth [228]* (19.8 °C, m= 12.36

to 0.01), and Good, Scott, Lacina, and McCullough

[229] (25 °C, m — 1.50 to 1.29).

L\ has been measured by Wilson and Miles [230]

(20 °C, extremely concentrated solutions), Roth

[231] (20 °C, m— 1.52), and Chedin and Dhers

[232] (25 °C, m= 151.0 to 6.64).

Forsythe and Giauque [68]* measured A//soln of the liquid monohydrate and trihydrate to final

molalities of 0.13 and 0.14 at 25 °C.

The chord area plot was used up to m — 5. The

resultant 4>l curve was accepted as such. In the

more concentrated region, another chord area plot was made using Thomsen’s, Berthelot’s, and Chedin

and Dher’s values. A preliminary curve of 4V

was then made which was adjusted by using the long

chords of Thomsen, Berthelot, and Forsythe and

Giauque and the dilute 4v curve. The greatest

weight was given to Forsythe and Giauque’s

measurements on the solution (dilution) of the liquid

monohydrate and trihydrate to m — 0.13.

ch2 o2 A//di in of aqueous formic acid has been measured

by Thomsen [30]* (19 °C, m = 111.01 to 0.28),

Berthelot [233] (8.5 °C, 777= 1.0 to 0.25), and

Faucon [234] (9 °C, m = 413 to 1). AHsoln as a function of concentration has been measured by

Glagoleva [235]* (25 °C, 777 = 677 to 0.52).

AHi of the reaction HCOOH(aq)^ H+ + HCOO-

, has been estimated from the Ka

’s given by Harned

and Owen [9]* and Everett and Wynne-Jones

[236]* and the AHn experiments of von Steinwehr

[192] and Canady, Papee, and Laidler [237]*.

The heat contribution due to ionization has been

calculated by using the Ka listed in Harned and

Owen [9] and incorporated into the 4v values.

The 4v values are to be used only with A//°(complete ionization).

c2 h4o2 A//diln of aqueous acetic acid has been measured

by Thomsen [30]* (19 °C, m= 111.01 to 0.28),

Berthelot [238] (23 and 24 °C, m = 2.78 to 0.35),

and [239] (8.5 °C, 777= 1.0 to 0.25), Faucon [234]

(7.4 °C, extremely concentrated solution to 777 = 0.88)

and Richards and Gucker [157]* (16 and 20 °C,

m = 2.22 to 0.07).

Li has been measured by Payn and Perman [212]

(20, 30, 40 to 70 °C, extremely concentrated solutions to m = 1.72).

A//soin as a function of concentration has been

measured by Klibanova and Nelman [240]* (24

°C, 7n = 538 to 0.77).

The AHi of C2 H4 02 was estimated to be —60 cal/

mole from the neutralization data of Thomsen [30]*

(18 °C, with NaOH, 77iC2H4o2 = 0.28), Canady, Papee,

and Laidler [237]* (25 °C, with NaOH, 77iC2H4o2 = 0.005), Richards and Mair [241]* (20 °C, with

NaOH, 77iC2H4O2 = 0.56), Berthelot [242] (9 °C, with

NaOH, 771^402 = 0,50), Arrhenius [194] (21.5 °C,

with NaOH), Lunden [243] (25 °C), Devoto [244],

Jordan and Dumbaugh [245], Graham [246], Favre

[247], and Andrews [248], and the Ka s and emf data

as fisted in Harned and Owen [9]*.

The heat contribution due to ionization has been

calculated and incorporated into the 4V table, which

is to be used only with the A//° for complete

ionization.

11

740-560 0 - 65-3
NH3 and NH4OH

AHmn has been measured by Thomsen [30]*

(19 °C, 777 = 17.34 to 1.11), Berthelot [249] (14 °C,

777 = 56.6 to 0.28), Calvet [250] (17 °C, 777 = 3.60 to

0.28), Ramstetter and Hantke [251] (20 °C, m = 2.56

to 0.14), Baud and Gay [252] (12.5 °C, m = 12.97 to

2.22), and Vrevskii and Zavaritskil [202, 214]* (14

°C, m= 18.50 to 0.28).

Vrevskii and Zavaritskil [202, 214]* (3, 19.9, 41,

and 61 °C, 777 = 53.89 to 0.44) measured A//soln as a function of concentration.

AHi is calculated as +865 cal/mole, by utibzing

the data of Pitzer [206]* (25 °C, reaction of NaOH

with NH4 CI in dilute solution), the neutralization

data of Thomsen [30]* (18 °C, with HC1 and HN03 , mNH4oH ~ 0.28), Berthelot [253] (20 °C with HC1,

77iNH40H = 0.50), [215, 220] (18 °C, with HCIO4, 777NH4oh = 0.25), and the Kb’ s at various temperatures and

emf data as tabulated by Harned and Owen [9]*.

Other neutralization measurements are those of

Bruni and Levi [254] (with HNO3 and HCIO4), Berthelot [242, 255] (with acetic acid), [216] (with

HCIO4), [256, 257] (with HNO3 and HC1), Biltz and

Messerknecht [258] (with HC1), Hess [259] (with HC1

and HNO3), Bouzat [260] (with HC1), Vorob’ev,

Privalova, Monaenkova, and Skuratov [261] (with

HCIO4), Favre and Silbermann [262] (with HC1 and

HNO3), Favre [247] (with HNO3, HC1 and acetic

acid), Andrews [263] (with unspecified acids),

[248] (with HC1, HNO3 , and acetic acid), Lunden

[243] (unspecified acids), Guntz [187] (with HF), and

Delepine [264] (with HC1). Moore and Winmill

[265] calculated the AHi from conductivity measure- ments and partition coefficients at various temperatures. The degree of ionization was calculated using the

value given by Harned and Owen [9] for Kb for

NH4OH. The heat contribution of the ionization

has been incorporated into the tabulated 3v values.

For convenience, the values are given for

NH4OH • 77H2O and NH3

• 77H2O. The 3v values

are to be used only with the value given for AH°x (complete ionization).

NH4CI

Ai/diln has been measured by Thomsen [30]*

(19 °C, 777 = 5.55 to 0.28), Pollok [266] (9 °C, one dilution of a saturated solution to m — 4), MondainMonval [267] (0.5 °C, one dilution from 777 = 5.55 to 0.19 and 18.1 °C, one dilution from m — 6.89 to 0.25)

and [268] (0 and 19 °C, one dilution of a saturated

solution to m = 0.37), Pratt [269]* (0 To 35.5 °C,

m = 2.22 to 0.14), Magie [270]* (3.7 and 22.3 °C,

m = 2.22 to 0.28), Fedorov and Sil’chenko [271]*

(22 °C, 777 = 7.12 to 0.28), and Streeck [272]* (25 °C,

m = 1.07 to 0.0002).

L\ has been measured by Dunnington and Hoggard [273] (20 to 25 °C, m = 5.05 to 2.31) and Rumelin

[274] (13 °C, 777 = 2.78 and 2.22).

AHsoin as a function of concentration has been

measured by Mishchenko and Ponomareva [92]*

(25 °C, 777 = 7.09 to 0.03), Fedorov and Sil’chenko

[271]* (22 °C, 777 = 0.56 to 0.14), and Winkelmann

[94] (17 to 28 °C, m = 6.23 to 0.58). von Stackelberg

[275] measured the differential heat of solution

(18 °C, 777 = 5.88 to 0.18).

The chord area plot was used. The greatest

weight was placed upon Streeck’s data in the dilute

region. The resultant 9+ curve was checked by

using the long chords of Thomsen, Fedorov and

Sil’chenko, Magie, Pratt, and Mishchenko and

Ponomareva.

NH4CIO4

The 3+ values given in the discussion of A//^.were

estimated, by considering the behavior of related

compounds and the AHn data of Berthelot [216]

(20 °C, m = 0.10) and Vorob’ev, Privalova, Monaenkova, and Skuratov [261]* (25 °C, 77iNH4 cio., = 0.14).

NH4Br

Only one measurement of the A//diln has been

reported, by Fedorov and Sil’chenko [271] (18 °C, one dilution from 771 = 7.71 to 0.28). The tabulated

values of 3>l have been estimated, by considering

the behavior of NH4 CI, HC1, HBr, NaCl, and NaBr.

NH4I The tabulated values of 3+ have been estimated.

NH4IO3

The 3V values given for A//° at 25 °C are estimated.

NH4NO3

A//djin has been measured by Thomsen [30]*

(18 °C, 771 = 22.20 to 0.28), Pratt [269]* (0 to 33.5 °C,

771 = 2.22 to 0.14), Mondain-Monval [276] (19 °C, one dilution of a saturated solution to 771 = 0.37)

and [267] (0 °C, 777=14.6 to 0.39), Federov and

Sil’chenko [271]* (21.5 °C, one dilution from m

= 24.13 to 0.28), Tollinger [97]* (21 °C, 777 = 18.50 to 0.56), Wassermann [277]* (18.2 °C, 777 = 22.21 to 0.55—0.14), von Wartenberg and Lerner-Steinberg

[278]* (18.2 °C, 777 = 22.21 to 0.56-0.24).

Li has been measured by Dunnington and Hoggard [273] (22.5 °C, 777 = 18.50 to 2.22) and Rumelin

[274] (11 °C, 777= 16.8 and 12 °C, 777 = 8.0). Fricke

and Havestadt [279] (0 °C, 777 = 15.13 to 1.63) meas- ured the vapor pressure of aqueous NH4NO3 from

which Li may be calculated.

The Ai/soin data of Fedorov and Sil’chenko [271]*

(21.5 °C, 777 = 0.56 to 0.14) have also been used for

the 3+ determinations.

The chord area plot was used below 777 = 1 . The

long chords were then used with the 3>l values

obtained to obtain 3+ for the more concentrated

solutions.

NH4C2H3O2

A//diln of aqueous ammonium acetate has been

measured by Thomsen [30]* (20 °C, 777 = 27.75 to 0.28), and Dunnington and Hoggard [273] (22.5 °C,

777= 18.50 to 2.28).

CH3NH2

A//diln has been measured by Bonnefoi [280]

(12 °C, one dilution from 777 = 0.50 to 0. 10).

12
AHsoln as a function of concentration has been

measured by Felsing and Wohlford [281]* (35 °C,

777 = 0.19 to 0.05). The dilution values at 35 °C in

this range are assumed to be relatively the same

as at 25 °C. Values of <3^ are given relative to m = 0.056.

(CH3)2 NH

AHsoi n as a function of concentration has been

measured by Patterson and Felsing [282]* (30 °C,

777 = 0.15 to 0.04). The scatter of their values permits only approximate estimates of <£/,, relative to m = 0.056.

(CH3)3 n

AHsoln as a function of concentration has been

measured by Patterson and Felsing [282]* (30 °C,

777 = 0.15 to 0.05). The scatter of their values permits only approximate estimates of relative to m = 0.056.

CH3NH3C1

A//dUn has been measured by Streeck [272]*

(25 °C, 777 = 0.52 to 0.0002) and Whitlow and Felsing [107]* (25 °C, 777 =1.02 to 0.04). The chord

area method was used to obtain preliminary values

of <f>L. These values were adjusted to fit Streeck’s

long chords.

(CH3)2 NH2 C1

A//diln has been measured by Streeck [272]*

(25 °C, 777 = 0.52 to 0.0002) and Whitlow and Felsing [107]* (25 °C, 777 = 1.01 to 0.05). The chord

area method was used to obtain preliminary values

of <£/,. These values were adjusted to fit Streeck’s

long chords.

(CH3) 3NHC1

AHdiln has been measured by Streeck [272]* (25

°C, 777 = 0.53 to 0.0002) and Whitlow and Felsing

[107]* (25 °C, m= 1.03 to 0.05). The chord area method was used to obtain preliminary values of <i>L- These values were adjusted to fit Streeck’s long

chords.

N(CH3 )4 C1

A//di in has been measured by Streeck [272]* (25

°C, 777 = 0.53 to 0.0004). The chord area method

was used to obtain preliminary values of <1>L . These

values were adjusted to fit Streeck’s long chords.

AgF

A//diln has been measured by Jahn-Held and Jel- linek [110]* (25 °C, m= 13.96 to 0.97). The tabulated values of are referred to 777 = 0.14, since

AgF is partially unionized and the association constants available are not sufficiently extensive to enable calculating the contribution of the ionization

to <t>L at greater dilutions. Equilibrium constants

have been given by Connick and Paul [283], Paul

[284], and Leden and Marthen [285].

AgC104 von Wartenberg [286] reported one measurement

(temperature unknown, m = 2Al to 1.0).

AgN03 Jackson, Smith, Gatty, and Wolfenden [287]*

made one measurement (25 °C, 777 = 0.37 to 0.17) of

A^fdjin- Terasaki [288] measured AHsoln as a function of

concentration (25 °C, 20 measurements, 777 = 1.09

to 0.02). There is an error in the way the concentrations are expressed. The concentrations were

corrected to the most reasonable form. The AHdiln were then used to determine <J>£. Although there is

still an error in the concentrations, it was felt that

the values obtained were reasonable and in line

with the <1>£ values of the other nitrates.

LiOH

A//dnn has been measured by Richards and Rowe

[70]* (16 and 20 °C, m = 2.22 to 0.14) and Ueda [289,

290]* (25 °C, saturated solution to 0.14). Juza and

Laurer [291] measured AHn of LiOH with HCI (20

°C).

The chord area method was used to obtain <t> L. These values were correlated with the emf data as given by Harned and Owen [9]*.

LiF

The <!>/, values were obtained from the AHdnn

measurements of Leighton [292]* (25 °C, 777 = 0.04

to 0.01) and Lange and Leighton [293]* (25 °C,

777 = 0.04 to 0.01) by using the chord area plot.

LiCl

A//diln has been measured by Tucker [42]* (15

°C, /7i=15.15 to 1.82), Naude [199]* (17.5 to 26 °C,

m— 1.0 to 0.0003), Nernst and Orthmann [294, 295]*

(18 °C, 77i = 0.10 to 0.001), Lemoine [296] (10 and

20 °C, 777= 16.62 to 0.49), Lange and Messner [297,

298]* (25 °C, one dilution from w. = 0.01 to 0.0014),

Richards and Rowe [70]* (16 and 20 °C, 777 = 2.22 to 0.14), Birnthaler and Lange [299] (25 °C, values on

graph from 777 = 18.32 to 0), Lange and Diirr [118]*

(25 °C, 777 = 19.88 to 0.63), and Monheim and Streeck

[300]* (25 °C, 777 = 0.28 to 0.05).

L\ has been reported by Dunnington and Hoggard [273] (22.5 °C, 777= 13.88 to 2.52) and Johnson

and Molstad [301] (30, 50, and 70 °C, 777 = 21.27 to

0.77).

A//soln as a function of concentration has been

measured by Lange and Diirr [118]* (25 °C, m

= 18.31 to 0.08).

LiC104 A//diln has been measured by Jones [302]* (25 °C,

777 = 3.98 to 0.007) and Austin and Mair [219]* (25

°C, one dilution from 777 =1.0 to 0.025). The chord

area method was used.

LiBr

A//diin has been measured by Lange and Schwartz

[119]* (25 °C, 777 = 17.92 to 0.07), Lange and Messner

[297, 298]* (25 °C, 777 = 0.03 to 0.001), Birnthaler

and Lange [299]* (25 °C, 777 =16.65 to 2.22), Mishchenko [303]* (25 °C, 777= 1.44 to 0.12), Lange and

13
Mishchenko [304]* (25 °C, one dilution from m — 1.44

to 0.13) and Pennington [305] (25 °C, equation for

the dilution of concentrated solutions from m = 17.3-11.5 to a dilute solution).

AHsoln as a function of concentration has been

measured by Lange and Schwartz [119]* (25 °C,

m= 17.12 to 0.22).

The chord area plot was used to obtain <6^.

Lil

The tabulated values of <I>l were estimated.

LiN02 Dode [306] measured AHn of LiOH with HN02 ; however, the concentration and temperature are uncertain.

LiNOs

Richards and Rowe [70]* measured AHdi \ n (20

°C, m — 2.22 to 0.14). <&L was obtained by the

chord area method.

Richards and Rowe [224] measured AHn of

LiOH with HN03 (16 and 17 °C, t77UN03 = 0.28).

This was used to check obtained by the chord

area method.

NaOH

A//diln has been measured by Thomsen [30]*

(19 °C, m = 18.50 to 0.56), Berthelot [307] (11 °C,

m = 21.6 to 0.12), [225] (9.5 and 24 °C, one dilution

from m — 6.3 to 0.66) and [233, 239] (8.5 °C, m= 1 to 0.13), Fricke [308]* (19 to 20 °C, 777 = 26.42 to 0.18), Calvet [250] (17 °C, 777 = 2.58 to 0.28), Sturtevant [50, 309]* (25 °C, 777 = 4. 18 to 0.004), Pratt [269]

(0 to 33.5 °C, m = 4.1 1 to 0.14), Sabatier [161, 310]

(17 °C, m— 11.10 to 0.14), Richards and Gucker

[157]* (16 and 20 °C, 777 = 2.22 to 0.02), Tucker [42]*

(17 to 22 °C, m = 20.91 to 5.36), Bertetti and McCabe

[311]

* (20 °C, 777 = 23.20 to 3.92), Richards and Rowe

[33]* (18 °C, one dilution from 777 = 9.49 to 1.28) and

[70] (16 and 20 °C, 777 = 9.64 to 0.14), de Forcrand

[312] (15 °C, one dilution of a saturated solution

to m=10.8) and [313] (20 °C, m = 0.5 to 0.13), and

Wilson and McCabe [125] (93.3 °C, m = 100 to 21.3).

Richards and Hall [314]* recalculated the dilution

data of Richards and Gucker with new specific

heat data.

Li, from vapor pressure measurements, has been

calculated by Payn and Perman [212] (20 to 70 °C,

m= 10.30 to 1.22) and Hayward and Perman [315]

(20 and 30 °C, m= 10.7 to 6.25).

The chord area method was used. Greater

weight was given in drawing the curves to Sturtevant’s data below m = 2, and to Bertetti and

McCabe’s data above that.

The calculated values of L2 check reasonably

well with Akerlof and Kegeles’ [126] emf values

below m = 12. In the very dilute region, m *£ 0.5,

the agreement with the emf results given by Harned

and Owen [9] is only fair. NaF

The tabulated ^>z, values are estimated on the

basis of a comparison of LiF, LiOH, KF, KOH,

and NaOH.

NaCl

A//diln has been measured by Scholz [316] (0 °C,

777 = 6.01 to 0.25), Sandonnini and Gerosa [141]

(18.5 °C, m — 6.07 to 0.44), Pollok [266] (9 °C, one

dilution of a saturated solution to m — 6), Backlund

[317] (17 °C, m = 4.40 to 0.37), Magie [270] (16.8

and 26.4 °C, 777 = 2.22 to 0.28), Pratt [269] (0 to 33.5

°C, m = 2.22 to 0.14), von Stackelberg [275] (0 and

18 °C, 777 = 4.40 to 0.56), Leitner [135] (20 °C, m= 5.55

to 0.56), van Deventer and van de Stadt [318] (one

dilution from m = 2.78 to 0.28), Naude [199, 319]*

(18 °C, m=1.0 to 0.001), Richards and Rowe [70]*

(20 °C, 7n = 3.2 to 0.19), Randall and Bisson [143]*

(25 °C, 777 = 6 to 0.4), Malcolm, Parton, and Watson

[320]* (25 °C, one dilution from 777 = 2.70 to 0.025),

Young and Machin [181]* (25 °C, 777 = 5.97 to 0.19),

Lange and Messner [297, 298]* (25 °C, one dilution

from 777 = 0.01 to 0.001), Robinson [321]* (25 °C,

777 = 0.10 to 0.0008), Gulbransen and Robinson [322]*

(25 °C, 777 = 0.82 to 0.005) in the form shown by

Young and Groenier [180], Young and Vogel [183]*

(25 °C, 777 = 6.15 to 0.05), and Monheim and Streeck

[300]* (25 °C, 777 = 0.32 to 0.06).

L\ has been reported by Riimelin [274] (14 °C,

777 = 2.78 and 2.22) and Dunnington and Hoggard

[273] (22.5 °C, 777 = 6.17 to 2.22).

The AHsoi n data of Lipsett, Johnson, and Maass

[323]* (20 and 25 °C, 777 = 5.92 to 0.04), Wiist and

Lange [21]* (25 °C, m = 5.62 to 0.52), and Benson and

Benson [324]* (25 °C, 777= 1.3 to 0.05), were used in

the chord area method, along with the measured

A//<iiin- The resultant <!>l curve was checked with

the other AHdm and AHsoln data. The agreement

was satisfactory.

The L2 values were checked with those given by

Harned and Owen [9] for combined calorimetic, emf

and boiling point data. The agreement is good below 777 = 2 and fair above.

NaClOa

AHdiln has been measured by Colomina and Nicolas [145]* (25 °C, one dilution from 777 = 9.05 to 0.43) and Lange and Robinson [325]* (25 °C, m = 0.10 to 0.0004). Colomina and Nicolas [145]*

(25 °C, 777 = 8.54 to 0.11) measured A//soln . NaC104 A//diln has been measured by Jackson, Smith,

Gatty, and Wolfenden [287]* (20 °C, one dilution

from 777 = 0.51 to 0.23), Colomina and Nicolas [145]*

(25 °C, 777 = 15.39 to 0.54), Austin and Mair [219]*

(25 °C, one dilution from m — 1.0 to 0.025), and Vanderzee and Swanson [221]* (25 °C, 777 = 1 1 .80 to 0.01).

A//soln has been measured by Colomina and Nicolas [145]* (25 °C, 777= 12.22 to 0.13).

The <1>l values were based primarily upon Vanderzee and Swanson’s measurements. Colomina

and Nicolas’ values above 777= 12 were coordinated

with them to complete the <1V curve.

14
NaBr

A//diln has been measured by Lange and Robin- son [326, 327]* (25 °C, 777 = 0.16 to 0.0025), van Deventer and van de Stadt [318] (16 °C, 777 = 8.20 to

0.28), Hammerschmid and Robinson [329]* (25 °C,

777 = 0.10 to 0.0003), Wiist and Lange [21]* (25 °C,

m = 9.16 to 1.10), and Wallace [328]* (25 °C, 777 = 9.00

to 0.25). Dunnington and Hoggard [273] (24 °C,

m — 4.27 to 2.52) measured L\.

A#soln has been measured by Wiist and Lange

[21]* (25 °C, m = 8.63 to 1.02).

NaBr03 The <!>£ values were obtained from Lange and Robinson’s [325]* A//dlln measurements (25 °C, 777 = 0.10

to 0.0004).

Nal

A//dnn has been measured by Thomsen [30]* (18

°C, m = 5.55 to 0.56), Wiist and Lange [21]* (25 °C,

m = 12.34 to 9.85), and Lange and Robinson [326,

327]* (25 °C, m *£ 0.1).

Wiist. and Lange [21]* measured AHsoln (25 °C,

m = 9.82 to 0.63)

NalOa

The <t>L values are based on Lange and Robinson’s

[325]* measurements of A//diln (25 °C, m = 0.1 to 0.0004).

NaN02 The values given are based on Perreu’s [149]*

measurements of A//diln (14 °C, 777 = 10.86 to 0.19). <&L was assumed to be +40 at m = 0.19, based on a comparison of the other Na+ electrolytes. The

scale, however, is subject to adjustment.

NaNOg

A//diln has been measured by Thomsen [30]*

(18 °C, 777 = 9.25 to 0.28), Pollok [266, 330] (9

CC, one dilution of a saturated solution to m — 5), von

Stackelberg [275] (0 and 17 °C, 777 = 8.88 to 0.28),

Bishop [331]* (25 °C, m = 2.17 to 1.50), Pratt [269]*

(0 to 33 °C, m — 2.22 to 0.14), Richards and Rowe

[70]* (16 and 20 °C, 777 = 2.22 to 0.14), van Deventer

and van de Stadt [318] (17 °C, one dilution from

m = 4.91 to 0.28), Stahlberg [332]* (18 °C, 777 = 7.40

to 0.19), Mondain-Monval [276]* (16 °C, m = 9.39

to 0.54), and [267, 268] (0 and 16 °C, one dilution of

a saturated solution to 0.37), Naude [199, 319]*

(11 and 18 °C, m — 0.33 to 0.001), and Lange an_d

Robinson [325]* (25 °C, 777 = 0.10 to 0.0002). L\

has been measured by Riimehn [274] (13 °C,

m = 8.71 to 0.55).

Below 77i = 0.1 the greatest weight in the chord

area plot was given to the measurements of Lange

and Robinson. The <E>/, values obtained in this

region were used in conjunction with the long chords

of the other investigators to adjust the <t>L values

obtained from the integration of the complete

d<i>rjdm112 plot.

NaC2H302

A//dnn has been measured by Thomsen [30]*

(19 °C, 771 = 5.55 to 0.56), Berthelot [333] (temperature unknown, one dilution from 771 = 0.50 to 0.25)

and [233] (8.5 °C, m = 0.50 to 0.25), Richards and

Gucker [157]* (16 and 20 °C, m— 2.22 to 0.03),

Perreu [153] (18 °C, 777 = 4.78 to 0.12), and Fricke

[308]* (19.5 °C, 777=14.92 to 0.28).

Fricke and Havestadt [279] (0 and 15 °C, m = 14.03

to 5.24) and Perreu [153] (18 °C, saturated solution)

measured L\.

NaCNS

A//dnn has been measured by Partington and

Soper [334]* (25 °C, 771 = 15.17 to 10.72). They

[334]* also measured AHsoln (25 °C, 777=15.25 to

0.28).

KF

A//diln has been measured by de Forcrand [335]

(15 °C, 777 = 14.23 to 0.25), Guntz [187, 336] (temperature uncertain, 777 = 2.0 to 0.50), Birnthaler

and Lange [337]* (25 °C, 777 =15.55 to 0.06), Lange

and Eichler [338]* (25 °C, m = 16.92 to 1.52), Messner

[339]* and Lange and Messner [340]* (777 = 0.21 to 0.004), and Monheim and Streeck [300] (25 °C,

777 = 0.30 to 0.06).

A//soin has been measured by Lange and Eichler

[338]* (25 °C, 777 = 3.16 to 0.21).

KOH

AHdiln has been measured by Thomsen [30]*

(20 °C, 777= 18.50 to 0.56), Berthelot [307]* (11.5

°C, 777= 18.14 to 0.25) and [225] (11.5 and 24 °C, one dilution from 777=1 to 0.5), Sabatier [310, 161]*

(17 °C, 777 = 13.88 to 0.21), de Forcrand [312] (15

°C, one dilution of a saturated solution to a dilute

solution), Pratt [269] (0 to 33.5 °C, 777 = 3.65 to 0.14),

Richards and Rowe [70]* (16 and 20 °C, 777 = 5.55

to 0.14), and Roth and Zeumer [341]* (20 °C, one measurement 777 = 0.83 to 0.03).

Biermann [342]* measured AHn of KOH with

HC1 (25 °C, 777 K0h = 16 to 3). A chord area plot of the dilution data was made to obtain preliminary values of <1+. These values were

adjusted to agree with the <I>z. values obtained from

Biermann’s neutralization data and with the emf

data in the dilute region as summarized by Harned

and Owen [8, 9]*.

KC1

A//di in has been measured by Stearn and Smith

[343] (25 PC, 777 = 3.16 to 0.18), Nernst and Orthmann [294, 295, 344]* (18 °C, 777 = 0.33 to 0.002),

Naude [109]* (12.2 and 17.8 °C, 777 = 0.33 to 0.007)

and [3191 (18 °C, 777 = 0.33 to 0.004), Richards and

Rowe [7( J* (16 and 20 °C, 777 = 2.22 to 0.14), Lange

and Leighton [345]* (12.5 and 25 °C, 777 = 0.50 to 0.002), Bishop [331] (25 °C, 777 = 4.49 to 0.06), Mondain-Monval [268] (18 °C, one dilution of a satu- rated solution to 777 = 0.37), Wiist and Lange [21]*

(25 °C, 777 = 4.82 to 0.57), Partington and Soper

[334]* (25 °C, 777 = 4.82 to 0.30), Pratt [269] (0 to 33.5 °C, 777 = 2.22 to 0.14), Magie [270] (3 and 21 °C,

777 = 2.22 to 0.28), van Deventer and van de Stadt

15
[318] (17 and 18 °C, m = 4.24 to 0.28), Pollok [266]

(9 °C, saturated solution to m = 3), von Stackelberg

[275] (0 and 18 °C, m = 2.22 to 0.28), Sandonnini and

Gerosa [141] (18.5 °C, m = 4.33 to 0.28), Scholz [316]

(0 °C, one dilution from m = 3.62 to 1.00), and Monheim and Streeck [300]* (25 °C, 777 = 0.30 to 0.06).

Li has been measured by Dunnington and Hoggard [273] (22.5 °C, 777 = 4.27 to 2.0), Riimelin [274]

(13.4 and 14.4 °C, 777 = 2.78 and 2.22), and Harrison

and Perman [346] (40, 50 to 80 °C, m = 4.29 to 1.21).

A//soln has been measured by Wiist and Lange

[21]* (25 °C, tti = 4.47 to 0.37) and Partington and

Soper [334]* (25 °C, 771 = 3.55 to 0.31).

KCIO3

The values are based on Andauer and Lange’s

[347]* measurements of A//diln (15 and 25 °C, m

= 0.10 to 0.0002).

Consideration was also given to von Stackelberg’s

[275] AHsoXn measurements (16 °C, 777 = 0.22 and

0.11) and differential heats of solution (16 °C, m = 0.50 to 0.22).

KCIO4

The <!>/, values are based on Andauer and Lange’s

[347]* measurements of A//diln (15 and 25 °C, m

= 0.10 to 0.0002).

KBr

A//diln has been measured by Berthelot [348] (11

°C, one dilution from 777 = 0.50 to 0.15), Scholz [316]

(0 °C, 771 = 4.0 to 0.25), Hammerschmid and Robin- son [329]* (25 °C, 77i = 0.10 to 0.0003), Wiist and

Lange [21]* (25 °C, 777 = 5.70 to 0.42), and Monheim

and Streeck [300]* (25 °C, 771 = 0.32 to 0.06).

Li has been measured by Dunnington and Hoggard [273] (22.5 °C, m = 5.55 to 2.05) and Riimelin

[274] (13.7 °C, 771 = 2.78 and 11.5 °C, 771 = 2.2).

A#soin has been measured by Wiist and Lange

[21]* (25 °C, 777 = 5.25 to 0.37).

KBrOa

The tabulated Ql values have been estimated.

KI

A//diin has been measured by Scholz [316] (0

°C, 777 = 3.99 to 0.15), Monheim and Streeck [300]*

(25 °C, 777 = 0.32 to 0.06), and Wiist and Lange [21]*

(25 °C, TT7 = 7.95_to 0.28); Dunnington and Hoggard

[273] measured Li (22.5 °C, 777 = 9.25 to 1.85).

AHso]n has been measured by Wiist and Lange

[21]* (25 °C, 777 = 8.97 to 7.34).

KIO3

The tabulated <1>l values were estimated considering the behavior of related compounds. The

A//diln measurements of Berthelot [216, 349] (13 °C,

777 = 0.5 to 0.13) and the differential heats of solution

of von Stackelberg [275] (16 °C, 777 = 0.28 to 0.11) were considered.

kc2 h3o2 A^diin has been measured by Thomsen [30]*

(19 °C, 777 = 11.10 to 0.28).

KNO3

A//dnn has been measured by Colson [350] (13.5

to 18 °C, 777 = 0.25 to 0.01 and from a saturated solution to 777 = 0.13), Naude [199]* (0, 12, 18, and 31

°C, 777 = 0.33 to 0.002) and [319]* (18 °C, 777 = 0.33

to 0.04), Lange and Messner [297, 298]* (25 °C,

777 = 0.01 to 0.009), Lange and Monheim [173]* (12.5

and 25 °C, 777 = 0.13 to 0.0006), Berenger-Calvet

[351]* (16 °C, one dilution from 777 = 0.78 to 0.06),

Mondain-Monval [268] (0 and 18 °C, one dilution

of a saturated solution to 777 = 0.37), Nernst and

Orthmann [294, 295, 344]* (18 °C, 777 = 0.10 to 0.0003), Richards and Rowe [70]* (20 °C, 777 = 2.22

to 0.14), Bishop [331]* (25 °C, 777 = 2.38 to 0.49),

Pratt [269]* (0 to 33.5 °C, 777 = 2.22 to 0.14), Federov

and Sil’chenko [271]* (22 °C, one dilution from m = 3.38 to 0.28), Scholz [316] (0 °C, 777= 1.0 to 0.13),

Pollok [266] (9 °C, one dilution of a saturated solution to 777 = 2), and Graham [352] (temperature un- known, 777 = 1 to 0.5).

L\ has been measured by Hunter and Bliss [353]

(30 °C, 777 = 2.55 to 1.12), and Riimelin [274] (13 °C,

777 = 2.29 and 1.67).

A/C^n has been measured by Berenger-Calvet

[351]* (16 °C, 777 = 2.49 to 0.09), von Stackelberg

[275]* (15 °C, 777 = 2.44 to 0.22) and Winkelmann [94]

(27.5 °C, 777 = 2.41 to 0.31).

Below 777 = 0.1 Lange and Monheim’s data were

given greater weight in the chord area plot. The

values obtained were adjusted above this molality by using the long chords.

KCNO

Myers [203]* and Vanderzee and Myers [204]* re- ported one dilution at 25 °C from 777 = 0.26 to 0.01.

However, this was insufficient upon which toffiase a &L curve. KCNS

AHmn has been measured by Partington and

Soper [334]* (25 °C, 777 = 23.96 to 15.6 and one dilution from 777 = 23.96 to 0.65). Hunter and Bliss

[353] measured L\ (30 °C, 777= 15.4 to 2.57).

Partington and Soper [334]* measured A//so i n (25 °C, 777 = 2.98 to 0.25).

The chord area plot was used below 777 = 3. The

long chord of Partington and Soper was used directly

with the $>l at 777 = 0.65 to determine <!>*, at m = 23.%.

This permitted the calculation of from A//diln down to 777= 15.6.

The intermediate region was estimated with the

aid of L\.

KM11O4

The <&l values were obtained from Perreu’s [174]*

measurements of A7/di i n (18 °C, 777 = 0.40 to 0.05).

RbF

The <I>z, values are based on Lange and Monheim’s

[173]* measurements of Ai/diln (25 °C, 777 = 0.21 to 0.0003).

RbCl

Monheim and Streeck [300] reported two measure16
merits of A//diln (25 °C, m = 0.32 to 0.08 and m = 0.32

to 0.06). However, their values on NaCl, KBr, KC1,

KF, and KI exhibit systematic deviations. These

measurements can therefore not be accepted. The

tabulated <$>l values were estimated on the basis of

the behavior of CsCl, KC1, and KBr.

RbBr, Rbl

The tabulated <f values were estimated on the

basis of the behavior of CsCl, KC1, KBr, and KI.

RbOH

de Forcrand [312] reported one measurement of

A//djin (15 °C, saturated solution to ra = 0.25).

de Forcrand [354] reported one measurement of

AHn of RbOH with HC1 at 15 °C. No concentrations were mentioned.

RbN03 The tabulated values were estimated on the

basis of the behavior of CsN03 , KN03 , and NaNQ3 . CsOH

de Forcrand [312]* reported one measurement

of A//diln (15 °C, saturated solution to m = 0.25).

Beketov [593] and de Forcrand [354] measured

AHn of CsOH with HC1 at 16 and 15 °C, respectively. No concentrations were given; therefore

the data cannot be used for the 4>L determinations

CsF

The tabulated values were estimated on the

basis of the behavior of KF and RbF.

CsCl

A//diln has been measured by Richards and Rowe

[70]* (16 and 20 °C, m=l.ll to 0.14), Lange and

Kohler [355]* (25 °C, below m = 0.25), Messner

[339]* (25 °C, below m — 0.25), and Monheim and

Streeck [300] (25 °C, two dilutions from m = 0.'S2 to 0.08 and from m = 0.32 to 0.06). Monheim and

Streeck’s measurements appear to have a sys- tematic error. CsBr and Csl

The tabulated 9>£, values were estimated on the

basis of the behavior of CsCl, KC1, KBr, and KI.

CsNOs The Q>l values are based on Richards and Rowe’s

[70]* measurements of A//diln (20 °C, m = 0.93 to 0.14).

Figure IX. AfOjJ/Am 14 versus m14 for NaCl at 25 °C.

The series of determinations are:

1 . Benson and Benson 25 °C A//sol „[324]

2. Wiist and Lange 25 ”0 AHMn [21]

3. Young and Vogel 25 °C A//dn„ [183]

4. Gulbransen and Robinson 25 °C A//dlln [322]

5. Robinson 25 °C AWdlln [321]

6. Young and Machin 25 °C A//dlln [181]

7. Lipsett, Johnson and Maass 25 °C A [323]

8. Lipsett, Johnson and Maass 20 °C A« m,„ [536]

9. Criss and Cobble 25 °€ [541]

10. Lange and Messner 20 °CA//dlln |297. 298]

11. Richards and Rowe 20 °C A//dlln [70]

17
FIGURE X. The relative apparent molal enthalpy, Ol, in call mole, as a function of m* at 25 °C in aqueous solutions o/HCl,

HC104 , HBr, HI, HN03 , NH4CI, NH4Br, NH4 I, NH4N03 , NH4 acetate, LiOH, LiBr, Lil, and LiN03 . Lil, NH4 Br, and NH4 I are estimated. The broken portion of the lines for HC10,

and LiNC>3 indicate the estimated values. Figure XII. <t* L as a function of in aqueous solutions of K, Rb, and Cs compounds at 25 °C. The curves shown for RbNC>3 and RbCl are estimated.

Figure XI. <I> L as a function of in ’4 in aqueous solutions of

NaOH, NaF, NaCl, NaBr, Nal, NaC103, NaC104 , NaBr03 , NaI03 , NaN03 , NaCNS,'an<i Na acetate, at 25 °C. NaF and NaBr03 are estimated.

Figure XIII. Ol as a function of in ’4 in aqueous solutions of

the hydroxides and chlorides of H, NH4, Li, Na, K, Rb, and Cs,

at 25 °C.

The curve for RbCl is estimated.

18
Figure XIV. <J> L as a function of 3

s 2.5 in aqueous solutions

at 25 °C.

VI. Heal of Neutralization

This discussion on AHn is limited to the determination of AHh; citations are given only for systems

considered in this determination. Wherever

AHn was used to determine $>i or AHi for a compound, reference is made to it in section V.

Rossini’s [3] procedure was used. All the data

utilized have been recalculated, using the newly

evaluated and values for the key components.

Only the most reliable data, for systems where <!>/. for all three components was well established, were

used to determine AH^.

Table XVII lists the measurements (and their

standard deviations) actually used for the final

evaluation. This was limited to NaCl, KC1, NaNO,3 , KNO3 , NaCKL, and to the work of Richards and

Rowe [224], Gillespie, Lambert, and Gibson [356],

Bender and Biermann [213], Pitzer [206], and

Vanderzee and Swanson [221, 357], despite the

presence of reliable data, such as those of

Richards and Rowe [224] on NaBr, Nal, KBr, KI,

LiCl, LiBr, Lil, and LiN03, Biermann and Weber

[223] on NaBr, and Biermann [342] on KC1, since

the <1>l values for HI, HBr, KOH, and LiOH were

uncertain at the concentrations used in the neutralization experiments. Once AH£ was established,

their results were used to help define these uncertain regions. There are two recent series of

measurements that require particular mention —

those of Papee, Canady, and Laidler [358] and

those of Bidinosti and Biermann [359]. Papee,

Canady, and Laidler’s measurements on the NaCl

system in a microcalorimeter give a value of — 13,490 ±50 cal/mole for AH£. The paper is not

sufficiently detailed to determine whether precautions were taken to remove CO2 from their dilute

acid solutions, what ratio of NaOH to HC1 was

used, and how the extrapolation to infinite dilution was made. Bidinosti and Biermann’s measure- ments on the NaCICL system give values for AH£

that range from —13,207 to —13,171 cal/mole between 1 and 3 molal HCIO4 and from —13,237 to — 13,300 cal/mole between 5 and 11 molal. There

is no explanation for these discrepancies.

The tabulated values result in the following:

Richards and Rowe, —13,346 ±30; Gillespie, Lambert, and Gibson, —13,363 ±50; Bender and Biermann, — 13,331 ±25; Pitzer, —13,366 ±25; and

Vanderzee and Swanson, —13,336 ±20 cal/mole.

The “best” value for AH°N ,25 °C, has been selected

as — 13,345 ± 25 cal/mole.

Using the values for HC1, NaOH, and NaCl at the various temperatures, A may be expressed,

in the range 15 to 30 °C, as (AH%)t =— 13,345

+ 53.5(£ — 25°) — 0.46p — 25)2

, or AH> of H2 0 as (AH°), = 13,345-53. 5(r - 25°) + 0.46(t - 25)2

. This equation differs from those of Rossini [3] and Pitzer [206], primarily because of d(ACp)/dT

which is now calculated to be 0.9 cal/mole deg in- stead of 0.3. The recent work of Ackermann [39,

122] indicates a greater variation of <!>£ of NaOH

with temperature than previously accepted.

The value for AH°h at 20 °C = 13,710 cal/mole,

given by Harned and Owen [9] from emf data, is 85

cal higher than that obtained by the use of the above

equation. The equation given by Harned and

Owen for the variation of AH° with temperature

indicates a value of 13,510 cal/mole at 25 °C. The

use of emf data for the heat of ionization involves

the first and second derivatives with respect to T. The value obtained this way is generally not as

reliable as that obtained calorimetrically.

Other measurements on the NaCl, NaNOs, KC1,

KNO3 , and NaC104 systems are as follows:

NaCl

AHn has been measured by Thomsen [30], Berthelot [255, 257], Berthelot and Louguinine [360], Hess

[361], von Steinwehr [192], Mathews [362], Mathews

and Germann [363], Ellingson [364], Favre [247],

Favre and Silbermann [262], Andrews [162, 248, 365],

Roth [186], Konnecke, Steinert, and Leibnitz [366],

Eley and Watts [367], Davies, Singer, and Stavely

[368], Schultz [369], Keyes, Gillespie, and Mitsukuri

[370], Douglas [371], Pitzer [206], Sacconi, Paoletti,

and Ciampolini [205], Myers [203], Muller [372],

Arrhenius [194], Lindner [373], Speakman and Stott

[374], Gillespie, Lambert, and Gibson [356], Bender

and Biermann [213], Olcott [375], Richards and

Rowe [224], and Papee, Canady, and Laidler [358].

NaC104 AHn has been measured by Thomsen [30], Berthelot [215, 216, 220], Vorob’ev, Privalova, Monaenkova, and Skuratov [261], and Bidinosti and Biermann [359].

740-560 0 - 65-4

19
NaNOg

The AHn has been measured by Thomsen [30],

Berthelot [257], Arrhenius [194], Hess [259], Andrews [248], Favre [247], Mathews and Germann

[363], Richards and Rowe [224], and Favre and

Silbermann [262].

KC1

AHn has been measured by Thomsen [30], Muller

[372, 376], Berthelot [257, 377, 378, 379], Hess [361,

380], Andrews [162, 248, 365], Favre and Silbermann

[262], Favre [247], Gillespie, Lambert, and Gibson

[356], Richards and Rowe [224], and Biermann [342].

KNOa

AHn has been measured by Thomsen [30], Berthelot [257], Graham [246], Hess [259], Andrews [162,

248, 365], Favre and Silbermann [262], Favre [247],

and Richards and Rowe [224].

VII. Heat of Solution at Infinite Dilution

The experimental data on A//soln were cor- rected to 25 °C, as explained earlier. The value of

A is obtained by using the relationship, AH° = A//soi n> m ~ L m

• A summary of the “best” values

of A//° for all the compounds can be found in table

XXI.

The discussion below lists the experimental data

(year reported, temperature of measurement,

number of measurements, and concentration

range), the values of A obtained and the “best”

value for each compound. Wherever information is not reported by the investigator, it is designated

by ?. KCl(c)

A//soln has been reported by a great many in- vestigators. As KC1 has been proposed as a standard for use in solution calorimetry and as, in many

cases, the older literature must be relied upon for

the values of A//soln of other compounds, all values

between 15 and 30 °C reported for KC1 have been

tabulated, together with the estimated uncertainties, (table XVIII). The values may be separated

into two distinct groups, AH£= 4,150 cal/mole as shown by Wiist and Lange [21] and A//°= 4,115

cal/mole.

The only apparent explanation at present, other

than systematic errors in measurements, is that of

variations in the treatment of the KC1 sample. The

“best” value of A//° has been selected as 4,115 ± 10

cal/mole, as indicated by the preponderance of data

in this region in the past 20 years.

Other measurements on KC1 besides those tabulated have been reported by Berthelot [225], Lange

and Monheim [173, 613], Yatsimirskii and Grafova

[437], Gire [438], Kaganovich and Mishchenko [439],

Favre and Silbermann [262], Lehtonen [440],

Zemczuzny and Rambach [441], Varali-Thevenet

[442], Ostwald [443], Scholz [316], Samoilov and

Buslaeva [444], Kessler and Gorbanev [445], Agostini [446], Richardson and Wells [447], Austin and

Mair [219], and Vrzhesnevskil [448].

HF(g)

AHsoln bas been measured by von Wartenberg

and Fitzner [449] (1926; 32 °C, 10 measurements, m = 0.14) and Roth [69] (1944; 20 °C, five measurements, m = 33.32 to 5.55). The values of A//° at 25

°C (complete ionization to H+ and F

_

) are — 14,700

and — 14,720 cal/mole, respectively. Khaldukov,

Linetskaya, and Bognovarov [450] have calculated

A/fsoin at m=0.14 from vapor pressure measurements. Their value corrects to — 14,817 cal/mole.

Guntz [187] has also measured A//soln . von Wartenberg and Fitzner corrected their ex- perimental values at m = 0.14 on the basis of the

presence of only the hexamer and monomer of HF

in the gaseous state. The more recent data and

calculations of Franck and Meyer [451], Smith

[452, 453], Spalthoff and Franck [454], Long, Hildebrand, and Morrell [455], Hu, White, and Johnston

[456], and Jarry and Davis [457] indicate the pres- ence of other polymer species. These more recent

data were used to recalculate the association factors

for the conditions of von Wartenberg and Fitzner’s

experiments. A value of —11,600 cal/mole was

obtained at m = 0.14, t — 25 °C, which leads to the

above value of —14,700 cal/mole. This is in excellent agreement with a value independent of the

polymerization of 14,690 cal/mole for the difference,

AHf HF(g) —

Hf F

_ (aqueous), obtained from the

work of Hood and Woyski [634] on the reaction of

NaCl(c) and HF(g) to form NaF(c) and HCl(g). It was not possible to recalculate Roth’s value.

By using the value for AHi selected in section V,

we obtain for AH° (no dissociation) —11,700 cal

mole, and A//° (compete ionization) =—14,700 ±200

cal/mole. The latter value is to be used with the

values of <I>l given in table XV, which include the

effects of the partial ionization and association.

HCl(g)

A//soln has been measured by Berthelot and Louguinine [458] (1875; 20 °C, four measurements,

m = 0.40 to 0.28), Thomsen [30] (1882; 19 °C, three

measurements, m = 0.20 to 0.14), Vrevskil and Zavaritskil [202, 214] (1923; 21.5 and 42 °C, 15 measurements, m = 4.83 to 0.19), Roth and Richter [459]

(1934; 21 °C, nine measurements, m = 0.09 to 0.006),

Roth and Bertram [460] (1937; 19 °C, seven measurements, m — 0.006 to 0.0002), Roth, Borger, and

Siemonsen [461] (1938; 20 °C, graph), Slansky [399]

(1940; 25 °C, ?, ?), Gunn and Green [462] (1962;

25 °C, five measurements, m = 0.02), and Vanderzee

and Nutter [652] (1963; 25 °C, 12 measurements,

m = 0.02). The values of AH° are: Berthelot and

Louguinine, —17,780 ±250; Thomsen, —17,760

±100; Vrevskil and Zavaritskil, —17,837 ±50;

Roth and Richter, — 17,940 ± 100; Roth and Bertram, — 17,810 ± 70; Gunn and Green, — 17,888 ± 15; Van20
derzee and Nutter, — 17,875 ± 12 cal/mole. Roth,

Borger, and Siemonsen’s extrapolated value corrects

to —17,950 cal/mole at 25 °C. Slansky gives a value of —17,820 cal/mole from his extrapolation.

Vanderzee and Nutter’s value, received after the

value selected for AH° was incorporated into the

revision of Circular 500, confirms the selection.

Measurements have also been made by Favre and

Silbermann [262], Abria [463], and Favre [464].

“Best” value, A//° =— 17,888 ± 15 cal/mole.

HC104(1)

AHsoi n has been measured by Krivtsov, Rosolovskil, and Zinov’ev [217] (1960; 25 °C, one measurement, m = 0.07), Rosolovskil, Krivtsov, and Zinov’ev

[465] (same measurement as first) and Berthelot

[215, 216] (1882; 19 °C, one measurement, m = 0.10).

The values of AH° are: Krivtsov et al., —21,215

±40; Berthelot, —20,570 cal/mole.

“Best” value, A//°= — 21,215 ±40 cal/mole.

HC104 H2 0(c)

A//S0] n has been measured by Krivtsov, Rosolovskil, and Zinov’ev [217] (1960; 25 °C, one measurement, m = 0.07); Arlman [466] (1939; one measurement, ?, ?), and Berthelot [215, 216, 220] (1882; 19

°C, one measurement, ?). Krivtsov’s value corrects to —7,875 ±40 cal/mole

for A//°. Arlman and Berthelot both report — 7,700 cal/mole for A//soln . “Best” value, AH°= — 7,875 ±40 cal/mole.

HBr(g)

AHsoln has been measured by Thomsen [30] (1883;

19 °C, three measurements, m = 0.15 to 0.11), Roth

and Bertram [460] (1935; 20.5 °C, 17 measurements,

m = 0.22 to 0.0005), Roth, Borger, and Siemonsen

[461] (1938; 20.5 °C, results given in graph), and

Vanderzee and Nutter [652] (1963; 25 °C, eight

measurements, m = 0.02).

The values of AH° are: Thomsen, — 20,290 ± 150;

Roth and coworkers, — 20,260±100; Vanderzee

and Nutter, — 20,350 ± 12 cal/mole.

Measurements have also been reported by Favre

and Silbermann [262], Ruff and Menzel [467], and

Berthelot [198].

“Best” value, AH°x = — 20,350 ± 12 cal/mole.

HI(g)

AHsoln has been measured by Berthelot and

Louguinine [458] (1875; 20 °C, three measurements, m = 0.12 to 0.06), Thomsen [30] (1883; 18 °C,

three measurements, m = 0.11), Roth, Borger, and

Siemonsen [461] (1938; 20 °C, results given in

graph, m = 0.006 to 0.0004), and Roth [69] (1944; seven measurements, m = 1.11 to 0.02). The values

of A//° are: Berthelot and Louguinine, — 19,850

± 300; Thomsen, — 19,390 ± 150; Roth, Borger,

and Siemonsen, —19,680; Roth, —19,520 ±50

cal/mole.

Measurements have also been made by Favre and

Silbermann [262] and Cottrell [468] (of HI(1)).

“Best” value, AH°=- 19,520 ±50 cal/mole.

HI03 (c)

AHsoln has been measured by Berthelot [216]

(1883; 12 °C, one measurement, m = 0.13), Thomsen

[30] (1883; 18 °C, two measurements, ra^O^S), and

Moles and Perez-Vitoria [394] (1932; 20.5 °C, four

measurements, m = 0.08). The values of AHsoln at 25 °C are: Berthelot, 2,060; Thomsen, 1,850 ±50;

Moles and Perez-Vitoria, 2,380 ±50 cal/mole.

Ditte [469] also measured AZ/soln . The specific heat of the solid used to correct to 25 °C was estimated. Since <&L is unknown, the

extrapolation to infinite dilution cannot be made.

“Best” value, A//soln = 2,100 ±300 cal/mole.

HNOad)

A//soin has been measured by Thomsen [30] (1882;

19 °C, ?, ra = 0.19), Forsythe and Giauque [68] (1942;

25 °C, four measurements, ra = 0.13), Karve [470],

and Hess [471]. The differential heat of solution

has been measured by Leclerc and Chedin [472]

and Chedin and Dhers [232].

The values of AH°x from the first two are: Thomsen, —7,850 ±100; Forsythe and Giauque,

—7,954 ±20 cal/mole.

“Best” value, AH°x=— 7,954 ± 20 cal/mole.

CH2 02 (1)

A//soln has been measured by Thomsen [30] (1883;

19 °C, one measurement, m=l.ll), Glagoleva [235]

(1936; 25 °C, 24 measurements, m = 677 to 0.52),

Berthelot [233,239], and Andre [473]. The values of

AHI, (complete ionization) from the first two are —204 ±20 cal/mole and —205 ±10 cal/mole, respectively.

By using the value for AHi selected in section V

we obtain for the best value, A//° (no ionization)

—175 ±10 cal/mole.

“Best” value, A//° (complete ionization) = —205

±20 cal/mole.

The latter value is to be used with the values of

<$>l tabulated.

C2 H402 (1)

AZ/goin has been measured by Berthelot [238]

(1875; 7 to 23 °C, three measurements, m = 2.78 to 0.35), Berthelot and Louguinine [458] (1875; 20 °C,

three measurements, m = 0.44 to 0.19), Thomsen

[30] (1883; 19 °C, two measurements, m — 2.78 and

1.11), Pickering [474] (1895; 13.6 to 18.5 °C, five

measurements, m = 0.28 to 0.14), Klibanova and

Nelman [240] (1933; 24 °C, 16 measurements,

115 to 0.77), and Pritchard and Skinner [475]

(1950; 21 °C, one measurement, m = 0.08). The

values of AH°x (complete ionization) are: Berthelot,

—350; Berthelot and Louguinine, —446; Thomsen,

—364; Pickering, —326; Klibanova and Neiman,

—347; Pritchard and Skinner, —361 cal/mole.

By using the value for AHi of C2 H4 02 determined

in section V we obtain:

21
“Best” value, A//° (no ionization) = —300

cal/mole.

“Best” value, AH°x (complete ionization) =—360

cal/mole.

The latter value is to be used with the <1+ values

which include the ionization contribution.

NH3 (g)

AHsoln has been measured by Thomsen [30] (1883;

19 °C, three measurements, m = 0.43 to 0.24),

Vrevskii and Zavaritskil [202, 214] (1924; 19.9 and

41 °C, 29 measurements, m — 34.05 to 0.61), and

Ramstetter and Hantke [251] (1931; 20 °C, five

measurements, m — 2.57 to 0.80). The values,

recomputed to A (complete ionization) are: Thomsen, —7,587 ±100; Vrevskii and Zavaritskil,

—7,443 ±40; Ramstetter and Hantke, —7,290 ±150

cal/mole.

Other measurements of AHsoln are those of

Vrevskii and Zavaritskil [202, 214] (3 °C and 61 °C),

Berthelot [249], Favre and Silbermann [262], Baud

and Gay [252], and Bouzat [260].

Vrevskii and Zayaritskil’s value is preferred;

however, as will be evident in the revision of Circular 500, Ramstetter and Hantke’s value is more

consistent with values obtained from other systems.

By using the value for AHi NH4 OH (AHi = +865 ±30 cal/mole) determined in section V we

obtain:

“Best” value, A//° (no ionization) = —8,160

cal/mole.

“Best” value, AH°x (complete ionization) = —7,290

±150 cal/mole.

The values of 3>z, given for NH4 OH and NH3 are

to be used only with AH

0^ (complete ionization).

NH4F(c)

Guntz [187] quotes a value of 1.5 kcal/mole from

Favre for the A//soln at 13 °C. The concentration is not mentioned. The reference cannot be located.

A/Coin— 1,500 cal/mole.

NH4 C1(c)

A//so i n has been measured by Winkelmann [94]

(1873; 17.2 to 28 °C, 10 measurements, m = 6.23 to

0.58), Berthelot [377, 476] (1873; 10 °C, one measurement, m = 0.46), Thomsen [30] (1883; 18 °C, two

measurements, m = 0.28), von Stackelberg [275]

(1898; 18 °C, three measurements, 771 = 0.74 to 0.37),

Colson [350] (1915; 14.9 and 22.3 °C, two measurements, 771 = 0.23), Mc-ndain-Monval [268] (1923; 18

°C, one measurement, m = 0.37), Nacken [477]

(1930; 20 °C, two measurements, m = 0.27), Drucker

[45] (1934; 18.1 °C, one measurement, 777 = 0.24),

Federov and Sil’chenko [271] (1937; 22 °C, three

measurements, m = 0.56 to 0.14), and Mishchenko

and Ponomareva [92] (1956; 25°C, 21 measurements,

771 = 7.09 to 0.03). The values of AH° are: Winkelmann, 3,560 ± 50; Berthelot, 3,400; Thomsen,

3,530 ±50; von Stackelberg, 3,586 ±50; Colson,

3,615 ± 100; Mondain-Monval, 3,498; Nacken,

3,623 ±75; Drucker, 3,528; Fedorov and Sil’chenko,

3,691 ± 100; Mishchenko and Ponomareva, 3,533

± 15 cal/mole. Measurements have also been

reported by Favre and Silbermann [262], Anderson

and Noyes [478], van Deventer and van de Stadt

[318], Lehtonen [440], Varet [479], and Andre [480].

“Best” value, A//° =3,533 ± 15 cal/mole.

NH4 C104(c)

AHso{n has been measured by Birky and Hepler

[481] (1960; 25 °C, six measurements, m — 0.009 to 0.001) and Vorob’ev, Privalova, Monaenkova, and

Skuratov [261] (1960; 25 °C, one measurement,

7n = 0.14). has been estimated as 10 and 0

cal/mole, respectively, at the concentrations mentioned above. The values of AH% are 8,020 ± 70

and 7,984 ±20 cal/mole, respectively.

Berthelot [216, 220] has also measured AHsoln . “Best” value, A//° = 8,000 ±40 cal/mole.

NH4 Br(c)

A//soin has been measured by Thomsen [30, 482]

(1877; 18 °C, four measurements, m — 0.28) and

Federov and Sil’chenko [271] (1937; 18°C, three

measurements, tti = 0.56 to 0.14). The values of

AH° are 4,064 ±50 and 3,920 ±50 cal/mole,

respectively.

Measurements have also been reported by Varet

[479] and Andre [480].

“Best” value, AH°= 4,010 ± 100 cal/mole.

NH4I(c)

AHsoi n has been measured by Thomsen [30] (1883;

19 °C, four measurements, 7n = 0.28) and Varet [479]

(1896; 18 °C, one measurement, ?). The specific

heat of the crystal used to correct to 25 °C was

estimated. From Thomsen’s measurements, AH°

is 3,280 ± 60 cal/mole.

“Best” value, A//°= 3,280 ±60 cal/mole.

NH4 I03(c)

A//soln has been measured by Kapustinskil,

Shidlovskil, and Shidlovskaya [483] (1958; 25 °C,

three measurements, m = 0.07) and Spencer and

Hepler [484] (1960; 25 °C, four measurements,

771 = 0.014 to 0.007). <1+ was assumed to be —20

and + 20 cal/mole, respectively. The values of AH°

are 7,590 ± 100 and 7,610 ± 100 cal/mole, respectively.

“Best” value, A//° = 7,600 ±70 cal/mole.

NH4 N02 (c)

AHsoln has been measured by Berthelot [485, 486]

(1874; 12.5 °C, one measurement, m = 0.13) and

Bureau [487] (1937; 20 °C, one measurement,

771 = 0.14). The specific heat of the solid and <I>c used to correct to 25 °C were estimated. <1+ has

been estimated as 60 cal/mole at the above concentrations. The values of AH°X are 4,300 and 4,610

cal/mole, respectively. Favre and Silbermann

[262] also report a measurement.

“Best” value, AH°X = 4,600 ±200 cal/mole.

22
NH4 NOl3 (IV)

AHsoin has been measured by Winklemann [94]

(1873; 16 to 22 °C, six measurements, m = 3.12 to 0.39), Tollinger [97] (1876; 19 to 25 °C, three measurements, ra = 0.56), Thomsen [488] (1878; 18 °C,

two measurements, ra = 0.28), Mondain-Monval

[267] (1925; 28 °C, one measurement, ra = 0.28),

Becker and Roth [489] (1934; 20 °C, seven measurements, ra = 0.05), and Fedorov and Sil’chenko [271]

(1937; 21.5 °C, three measurements, m = 0.56 to

0.14). The values of AH°x are: Winkelmann,

6,125 ±100; Tollinger, 6,040 ±100; Thomsen,

6,117 ±50; Mondain-Monval, 5,990; Becker and

Roth, 6,093 ±40; Fedorov and Sil’chenko, 6,216 ±50

cal/mole.

Other measurements of A//soln are those of

Berthelot [377], van Deventer and de Stadt [318],

Favre and Silbermann [262], Cohen and Helderman [490, 491], Cohen, Moesveld, and Helderman

[492], and Mondain-Monval [268, 493].

“Best” value, A//* = 6, 140 ±50 cal/mole.

NH4 C2 H3 02 (c)

AHsoln has been measured by Berthelot [494]

(1873; 24 °C, one measurement, m — 0.28). His

value, recomputed to 25 °C, infinite dilution, and no

hydrolysis, is —570 ±200 cal/mole.

<&l as tabulated includes the hydrolysis effect.

NH4 CN(c)

A//soln has been measured by Berthelot [377]

(1875; 18 °C, one measurement, ra = 0.06) and [216,

495] (1871; ?, one measurement, m = 0.13). The

ACp for correction to 25 °C has been estimated. <6^ has been estimated as —15 cal/mole at m = 0.06.

AHI, from Berthelot’s first value is 4,200 ±250

cal/mole.

“Best” value, AH°X = 4,200 ±250 cal/mole.

NH4CNS(c)

A//soin has been measured by Joannis [496] (1882;

12 °C, four measurements, ?). We have assumed

the concentration to be /n = 0.56, and <I>L to be 30

cal/mole. A/7* is 5,400 ±200 cal/mole.

“Best” value, AH° = 5,400 ± 200 cal/mole.

CH3 NH2(g)

A//soln has been measured by Aston and Ziemer

[108] (1946; 25 °C, five determinations, m = 0.104),

Felsing and Thomas [497] (1929; 25 or 30 °C, seven

determinations, m — 0.16 to 0.06), Felsing and

Wohlford [281] (1932; 35 °C, 12 determinations,

m = 0.19 to 0.05), and Bonnefoi [280] (1901; 12 °C,

two measurements, m — 0.09).

Aston and Ziemer’s measurements on CH2 NH2(1) were corrected to CH3NH2(g). Their corrected

value for A//soln> m =0 .io4 , —11,167 ±57 cal/mole, has

been corrected to A//soln>m = 0.0555- There appears to be a systematic error in Felsing’s measurements.

The data are insufficient to warrant extrapolation

to infinite dilution.

“Best” value, A//soln> m=o.o.555 =— 11,290 ± 75 cal

/

mole.

(CH3)2 NH(g)

A//soln has been measured by Patterson and

Felsing [282] (1938; 30 °C, 15 measurements,

m = 0.15 to 0.04). Their values were corrected to 25 °C; however, the random scatter of the values

permits only an approximate value of A//soln> m = 0.056, =— 12,900 ± 200 cal/mole. Extrapolation to infinite

dilution is not possible.

(CH3) 3 N(g)

A//soln has been measured by Berthelot [498]

(1880; 20 °C, one determination, m = 0.21) and

Patterson and Felsing [282] (1938; 30 °C, 15 measurements, m = 0.15 to 0.05). The values were corrected

to 25 °C; however, the random scatter of the values

permits only an approximate value of A//solni = 0.056 = — 12,800 ±200 cal/mole.

CH3 NH3C1(c)

A//soln has been measured by Aston and Ziemer

[108] (1946; 25 °C, four determinations, m = 0.12 to 0.10). The value of AH° is 1,378 ±15 cal/mole.

“Best” value, A//° = 1,378 ± 15 cal/mole.

(CH3)3NHC1(c)

A//soln has been measured by Berthelot [498]

(1880; 18 °C, one determination, m = 0.21). The

specific heat of the crystal used to correct to 25 °C

has been estimated. AH°x = 340 ± 200 cal/mole.

Tentative “Best” value, A//° = 350 ±200 cal/mole.

N(CH3) 4 C1(c)

A//soln has been measured by Askew et al., [499]

(1934; 20 °C, two determinations, ra = 0.01). The

ACp used to correct to 25 °C was estimated. AH° = 975 ±75 cal/mole.

“Best” value, A//° = 975 ±75 cal/mole.

N(CH3 )4 Br(c)

AHSoin has been measured by Samoilov [407, 408]

(1951; 25 °C, one measurement, m = 0.06) and Askew

et al., [499] (1934; 20 °C, three measurements,

m = 0.01 to 0.006). The ACp used to correct to 25

°C was estimated, has been estimated as 10

and 25 cal/mole, respectively. The values, recom- puted to infinite dilution and 25 °C, are 5,430 and

5,800 ± 100 cal/mole, respectively.

“Best” value, AH^ — 5,800 ±100 cal/mole.

N(CH3)4I(c)

AHsoln has been measured by Walden [500] (1907;

19 to 20 °C, two determinations, m — 0.22 and 0.13)

and Coulter, Pitzer, and Latimer [109] (1940; 25 °C,

five determinations, m = 0.06 to 0.04). The latter

investigators also measured the specific heat of the

crystal; <l>c was estimated. <!>/, has been estimated

as —120 and 10 cal/mole, respectively. The

values of AH°x are 10,080 ±100 and 10,055 ±20 cal/

mole, respectively.

“Best” value, A//^ = 10,055 ±20 cal/mole.

23
AgF • fiH20(c)

Guntz [187, 501] has measured A//soi n of AgF

(1884; 10 °C, A//dilute solution =~d,400 cal/mole) and

AgF • 2Hz O, (10 °C, A//dilute solution = 1,500 cal/mole).

Guntz and Guntz [502, 503] measured A//soln of

AgF (1913; 16 °C, A//di i ute solution =—4,300 cal/mole),

AgFH2 0 (10 °C, A//dilute solution =—850 cal/mole),

AgF-2H2 0 (10 °C, A//di iute solution = 1,500 cal/mole),

and AgF-4H2 0 (13 °C, solution = 4,930 cal

mole).

“Best” values cannot be given at the present time

since there is insufficient information available.

AgC104(c)

AHgoin ^as been measured by Bruni and Levi

[254] (1917; 12 °C, one measurement, 777 = 0.06).

The ACp used to correct to 25 °C was estimated.

has been assumed to be —100 cal/mole. The

value of AH°x is 1,760 ±150 cal/mole.

“Best” value, A//^, = 1,760 ±150 cal/mole.

AgN02 (c)

AHsoin has been measured by Berthelot [216]

(1883; ?, one measurement, ?) and Bureau [487]

(1937; 20 °C, one measurement, 777 = 0.14). 4>l has

been estimated as —20 cal/mole at 777 = 0.14.

Berthelot reports A//soi n = 8,740 cal/mole. Bureau’s

value, recomputed to infinite dilution and 25 °C, is 8,830 cal/mole.

“Best” value, A/f° = 8,830 ±200 cal/mole.

AgN03(c)

AHsoin has been measured by Thomsen [30] (1883;

18 °C, two measurements, 777 = 0.28), Lange and

Martin [397] (1937; 25 °C, one measurement,

m = 0.12). Smith, Brown, and Pitzer [504] (1937;

25 °C, one measurement, m = 0.009), Roth [69] (1944;

17.4 to 19 °C, four measurements, m = 0.08 to 0.03),

Graham and Hepler [505, 506] (1955; 25 °C, six measurements, 777 = 0.06 to 0.004), and Terasaki [288]

(1957; 25 °C, 20 measurements, 777 = 1.09 to 0.02).

The values of AH°x are: Thomsen, 5,377 ±50; Lange

and Martin, 5,475; Smith, Brown, and Pitzer,

5,365 ±50; Roth, 5,428 ±50; Graham and Hepler,

5,440 ±50; Terasaki, 5,485 ±100. Although the

concentrations in Terasaki’s paper were corrected

to the most reasonable form, it was not possible to completely eliminate the errors. Measurements have also been made by Berthelot

[377], Favre and Silbermann [262], and Bruni and

Levi [254].

“Best” value, Ai/^ = 5,400 ±50 cal/mole.

LiOH(c)

A//soln has been measured by de Forcrand [507,

508] (1907; 15 °C, one measurement, 777 = 0.50),

Ueda [289, 290] (1933; 25 °C, four measurements,

777 = 0.14), and Reshetnikov [429] (1961; 25 °C, seven measurements, 777 = 0.14). The values of A//° are: de Forcrand, —4,990; Ueda, —5,040; Reshetnikov,

—5,632 ±15 cal/mole.

Truchot [509] has also reported a measurement.

“Best” value, A//^ =—5,632 ±15 cal/mole.

LiOH H2 0(c)

A//soin has been measured by de Forcrand [510]

(1906; 18 °C, one measurement, 777 = 0.50) and [508]

(1908; 15 °C, one measurement, 777 = 0.50), and Ueda

[289, 290] (1933; 25 °C, three measurements,

777 = 0.14). The values of AH° are: de Forcrand, — 1,100 and —950; Ueda, — 1,020±200 cal/mole.

The dissociation pressure measurements of Ueda

[290] lead to a value of AH for LiOH(c) + H2 0(l) = LiOH • H2 0(c) in poor agreement with that calculated from the A//° values of the two solids, if AH° =—1,020 cal/mole is used. The value is in excellent agreement, though, with that calculated using

de Forcrand’s measurements on LiOH(c) and

LiOH-H2 0(c). We have combined this difference

with the value for LiOH(c) to obtain the “best”

value.

“Best” value, AH°=— 1,600 ±400 cal/mole.

LiF(c)

A//soln has been measured by Kapustinskil and

Stakhanova [511] (1956; 25 °C, ?, ?) and Kolesov and

Skuratov [512] (1961; 21.5 °C, 15 measurements,

777 = 0.01). de Forcrand [513] thought he measured

AHsoln of LiF(c); solubility measurements indicate

this was not possible, since his compound was much

more soluble. Kapustinskil and Stakhanova give a value at infinite dilution of — 1,330 cal/mole.

Kolesov and Skuratov’s measurements correct to 1,130 ±25 cal/mole. The solubility measurements

of Payne [514] indicate that the differential heat of

solution at saturation is positive.

“Best” value, A//° = 1,130 ±25 cal/mole.

LiCl(c)

AHso\ n has been measured by Thomsen [30] (1883;

18.5 °C, three measurements, 777 = 0.28 to 0.19),

Pickering [515] (1888; 18 °C, one measurement,

777 = 0.28), Bonnefoi [280, 516] (1897; 15 °C, one meas- urement, 777 = 0.25), Haigh [388] (1912; 21 °C, three

measurements, 777 = 0.14), Lange and Diirr [118]

(1926; 25 °C, 78 measurements, 777= 18.34 to 0.04),

Maier [517] (1927; 19.5 °C, one measurement,

777 = 0.24), Wassermann [277] (1930; 18.3 °C, four

measurements, 777 = 0.12 to 0.08), Askew et al., [499]

(1934; 20 °C, one measurement, 777 = 0.04), Lange

and Martin [397] (1937; 25 °C, one measurement,

777 = 0.20), Samoilov [407, 408] (1951; 25 °C, one measurement, 777 = 0.06), and Samoilov and Buslaeva [444] (1960; 25 and 35 °C, three measurements,

777 = 0.06). The values of AH°x are: Thomsen,

—8,704 ±50; Pickering, —8,500 ±100; Bonnefoi,

—8,847; Haigh, —8,700 ±50; Lange and Diirr,

—8,813 ±40; Maier, —8,670; Wassermann, —8,884

±30; Askew et al., —8,690; Lange and Martin, — 8,963; Samoilov, —8,780; Samoilov and Buslaeva,

—8,790 ±100. The precision of Lange and Durr’s

values is excellent. The overall uncertainty should

be ±10; however, there appears to be a systematic

error in the measurements as shown by their specific

heat measurements. In considering this, the

“best” value has been estimated as A//° =— 8,850

±50 cal/mole.

24
“Best” value, A//° = — 8,850 ± 50 cal/mole.

LiCl H2 0(c)

AHSoin has been measured by Bogorodskii [518]

(1911; 18 to 23 °C, four measurements, ra = 0.40 to 0.28) and Maier [517] (1927; 19.5 °C, one measurement, m = 0.17). These values correct to —4,540

±100 and —4,590 cal/mole, respectively.

The measurements of Ueda [290], Maier [517],

Appleby and Crawford [636], and Hiittig and

Reuscher [637] on the dissociation pressure of

LiCl • H2 0(c) lead to a value of AH for the reaction,

LiCl(c) + H2 0(1) = LiCl • H2 0(c), in good agreement

with the difference, A//° LiCl(c) — A LiCl • H2 0(c).

“Best” value, A//° = — 4,560 ± 100 cal/mole.

LiCl 2H2 0(c)

AHS0\ n has been measured by Bogorodskii [518]

(1911; 18 to 23 °C, four measurements, m = 0.39 to

0.34). However, Campbell and Griffiths [638]

reported the transition, LiCl • 2H2 0(c) = LiCl • H2 0(c) occurred at 12.5 °C.

Hiittig and Reuscher’s [637] measurements of

the dissociation pressure lead to a value of AH

for the reaction, LiCl • H2 Q(c) + H2 0(1) = LiCl • 2H2 0(c), in excellent agreement with the difference

AHI LiCl • H2 0(c) - AHI LiCl • 2H2 0(c).

Assuming that the compound exists at 25 °C,

we have, as “best” value, A//° =— 1,120 ± 40 cal/

mole.

LiC104(c)

AZ/Soi n has been measured by Smeets [395] (1933;

18 °C, two measurements, m = 0.24), Markowitz,

Harris, and Stewart [519] (1959; 25 °C, one measurement, m = 0.12), Birky and Hepler [481] (1960; 25 °C,

nine measurements, m — 0.02 to 0.005), and

Vorob’ev, Privalova, Monaenkova, and Skuratov

[261] (1960; 25 °C, one measurement, m = 0.13).

The ACP used to correct to 25 °C has been estimated.

The values correct to: Smeets, —6,511 ±75;

Markowitz et al., —6,364 ±50; Birky and Hepler, — 6,325 ±50; Vorob’ev et al., —6,414 ±60 cal/mole.

“Best” value, AH°=— 6,345 ±50 cal/mole.

LiC104 3H20(c)

AHS0\ n has been measured by Smeets [395] (1933;

18 °C, two measurements, m — 0.17) and Markowitz,

Harris, and Stewart [519] (1959; 25 °C, one measurement, m = 0.12). The ACp used to correct to 25 °C

has been estimated. Their values correct to 7,896

± 75 and 7,795 ± 50 cal/mole.

“Best” value, A//° = 7,795 ± 50 cal/mole.

LiBr(c)

A//soln has been measured by Bodisko [520] (1889;

17 °C, one measurement, m = 0.34), Bonnefoi [521]

(1900; 14 °C, one measurement, m = 0.34), Maier

[517] (1927; 17 °C, one measurement, m = 0.12), and

Lange and Schwartz [119] (1928; 25 °C, 44 measurements, m= 17.12 to 0.22). Their values of AH°

are: Bodisko, —11,645 ±75; Bonnefoi, —11,830

±100; Maier, —11,850; Lange and Schwartz, — 11,668 ±50. The precision of Lange and

Schwartz’ measurements is excellent; the standard

deviation is ± 3. In view of the apparent systematic

error in their specific heat measurements, the

uncertainty in their solution measurements has been

increased to ±50 cal/mole.

“Best” value, AH° =— 11,670 ± 50 cal/mole.

LiBr-H2 0(c)

A//soln has been measured by Maier [517] (1927;

17 °C, one measurement, ra = 0.10). His value

corrects to — 5,555 cal/mole.

Maier’s measurements of the dissociation pres- sure of LiBr-H2 0(c) lead to a AH for the reaction,

LiBr(c) + H2 0(1) = LiBr-H2 0(c) in good agreement

with the difference, AH° LiBr(c) — AH° LiBr-H2 0(c).

“Best” value, AH°= — 5,560 ± 100 cal/mole.

LiBr-2H2 0(c)

A//soi n has been measured by Maier [517] (1927;

17 °C, one measurement, m = 0.08). The value of

AH° is —2,250 cal/mole.

Maier’s measurements of the dissociation pres- sure are discordant and cannot be used. Hiittig

and Reuscher’s [637] measurements lead to a AH for

the reaction, LiBr-H2 0(c) + H2 0(1) = LiBr-2H2 0(c),

which is in poor agreement with the difference

AHI LiBr • H2 0(c) - AHI LiBr • 2H2 0(c).

“Best” value, AH°=— 2,250 ±200 cal/mole.

LiBrOs(c)

AHS0\ n has been measured by Boyd and Vaslow

[522] (1962; 25 °C, three measurements, m = 0.007).

has been estimated to be 30 cal/mole at this

concentration. AH° is 338 ±40 cal/mole.

“Best” value, A//°=340±40 cal/mole.

Lil(c)

AHso\ n has been measured by Bodisko [523, 524,

525] (1888; 17 °C, one measurement, m = 0.18),

Mosnier [526] (1897; 15 °C, one measurement, m = 0.07), Beketov and Beketov [527] (1902; 18 °C,

two measurements, m = 0.24), and Maier [517] (1927;

17 °C, one measurement, m = 0.07). Beketov’s

measurements were on a mechanical mixture of

Lil with NaCl and KC1. The values of AH°x are Bodisko, — 15,100 ± 100; Mosnier, — 15,280 ± 150;

Beketov, — 15,030 ± 150; Maier, — 15,130 ± 100.

“Best” value, A//° = — 15,130± 75 cal/mole.

Lil H2 0(c)

AHS0\ n has been measured by Maier [517] (1927;

17 °C, one measurement, m = 0.07). The value

corrects to — 7,090 ± 100 cal/mole.

The dissociation pressure measurements of

Maier [517] and Hiittig and Pohle [639] lead to a AH for the reaction, Lil(c) + H2 0(1) = Lil • H2 0(c),

in fair agreement with the difference AH°x Lil(c)

-AHI Lil - H2 0(c). “Best” value, A//° =- 7,090 ± 200 cal/mole.

25
Lil 2H2 0(c)

A//soi n has been measured by Maier [517] (1927;

17 °C, one measurement, 771 = 0.06). His value

corrects to — 3,530 ± 100 cal/mole.

Maier’s dissociation pressure measurements

lead to a AH for the reaction Lil • H2 0(c) + H2 0(1) = Lil • 2H2 0(c), in good agreement with the dif- ference, AHI Lil • H2 0- A//° Lil • 2H2 0.

“Best” value, A//° =— 3,530 ± 100 cal/mole.

Lil 3H2 0(c)

Maier [517] (1927; 17 °C, one measurement, m

= 0.05) measured AHsoXn . The value corrects to 140 cal/mole.

Maier’s dissociation pressure measurements

lead to a AH for the reaction, Lil • 2H2 0(c)

+ H2 0(l) = LiI*3H 2 0(c) that is impossible. We

have therefore based A//° on the calorimetric value.

“Best” value, A//° = 140 ± 100 cal/mole.

LiN02 (c)

AHsoin has been measured by Dode [306, 528]

(1936; 12 °C, three measurements, 777 = 0.13) and

Bureau [487] (1937; 20 °C, one measurement, m

= 0.14). The ACP used to correct to 25 °C has

been estimated. O/, has been estimated to be 130

cal/mole at the above concentrations. The values

of A//° are —2,636 and —2,625 cal/mole, respectively.

“Best” value, A//° =— 2,630 ± 100 cal/mole.

LiN02

• H2 0(c)

Bureau [487] (1937; 20 °C, one measurement, m

= 0.14) has measured AHsoln . The ACp used to correct to 25 °C has been estimated. has been

estimated as 130 cal/mole at this concentration.

The value corrects to 1,680 cal/mole.

Ray and Ogg [640] reported one measurement of

the dissociation pressure at 25 °C. This information is insufficient to use as corroborating evidence

for the difference, A//° LiN02(c) — A//° LiN02

• H2 0(c). The “best” value has been based solely on Bureau’s measurement.

“Best” value, A//°= 1,680 ±200 cal/mole.

LiN03(c)

AZ/goin has been measured by Thomsen [30] (1883;

20 °C, two measurements, 777 = 0.56), Pickering

[515] (1888; 18 °C, one measurement, 777 = 0.27),

and Haigh [388] (1912; 21 °C, three measurements,

777 = 0.12). The values of AH° are: Thomsen, — 574 ± 50; Pickering, — 626; and Haigh, — 630 ± 50

cal/mole.

“Best” value, A//° = — 600 ±40 cal/mole.

NaOH(c)

AHso\ n has been measured by Thomsen [30] (1883;

17 °C, four measurements, m = 0.34 to 0.29), Berthelot [307] (1875; 10.5 °C, two measurements, m = 0.36), de Forcrand [529] (1902; 21.5 °C, one measurement, 777 = 0.35), Roth, Wirths, and Berendt

[124] (1942; 20 °C, two measurements, m = 10.11 and

0.13), Bobtelsky and Lairsch [530] (1950; 23 °C, one

measurement, 777 = 0.25), Reshetnikov [429] (1961;

25 °C, five measurements, 777 = 0.14), and Murch and

Giauque [531] (1962; 25 °C, five measurements,

777 = 0.30). The values of AH° are: Thomsen, — 10,320; Berthelot, — 10,410; de Forcrand, — 10,540;

Roth and coworkers, — 10,400; Bobtelsky and

Lairsch, —10,190; Reshetnikov, —10,555 ±20

cal/mole. Murch and Giauque’s value of — 10,637

± 10 cal/mole was obtained from the extrapolation of

their measurement on solid NaOH • nH2 0 where n

varied from 0.97 to 0.12. We have accepted their

value.

“Best” value, AH° =- 10,637 ± 10 cal/mole.

NaOH H2 0(c)

A//soln has been measured by Pickering [532]

(1895; 19 °C, two measurements, m— 0.30 and 0.19),

de Forcrand [529] (1902; 21.5 °C, one measurement,

m = 0.35), and Murch and Giauque [531] (1962; 25

°C, five measurements, 777 = 0.30). The corrected

values are —5,380 ±200, —5,400, and —5, 118 ±10

cal/mole, respectively. Murch and Giauque’s value was obtained as for the anhydrous NaOH. We

have selected their value.

“Best” value, A//° = — 5,118 ± 10 cal/mole.

NaF(c)

AHsoln has been measured by Guntz [187] (1884;

12 °C, one measurement, 777 = 0.14), Hepler, Jolly,

and Latimer [533] (1953; 25 °C, one measurement,

ra = 0.04), and Latimer and Jolly [534] (1953; 25 °C,

two measurements, 777 = 0.04 and 0.02). The values

of AH° are: Guntz, 130; Hepler, Jolly, and Latimer,

210; and Latimer and Jolly, 220 cal/mole.

de Forcrand [335] quotes a value which may have

been taken from Guntz.

“Best” value, A//° = 218±10 cal/mole

NaCl(c)

The values of AH° are shown in table XIX. Other

measurements of the heat of solution have been

reported by: Lehtonen [440], Scholz [316], Staub

[542, 543], Berthelot [544], Berthelot and Ilosvay

[383], Kessler and Gorbanev [445], Ostwald [443],

Richardson and Wells [447], Bronsted [385], Sandonnini and Gerosa [141], Mishchenko and Yakovlev [545], Favre and Silbermann [262], Graham

[246], Varali-Thevenet [442], von Stackelberg [275,

614], Zemczuzny and Rambach [441], Varet [479],

Jones, Burgess, and Amis [546], Chipman, Johnson,

and Maass [133], Allmand and Polack [547], and

Koehler [612].

“Best” value, A//°=928±5 cal/mole.

NaC102 (c)

AHsoln has been measured by Fontana and Latimer [548] (1949; 25 °C, two measurements, m = 0.005), Levi and Bisi [549] (1956; 25 °C, three measurements, dilute solution), and Ishi [550] (1961; 18

°C, two measurements, 777 = 0.06). The ACp used

to correct to 25 °C has been estimated. <!>/, has

been estimated as 25 cal/mole at m — 0.005 and 50

cal/mole at tti = 0.06. Fontana and Latimer’s value

26
corrects to 80 ± 10 cal/mole at infinite dilution.

Ishi’s value corrects to — 20 ± 100 cal/mole at infinite

dilution. Levi and Bisi give a value of 370 cal/mole

for their “dilute solution.”

“Best” value, A//° =80± 10 cal/mole.

NaC102 3H2 0(c)

AHS0in has been measured by Levi and Bisi [549]

(1956; 25 °C, three measurements, dilute solution)

and Ishi [550] (1961; 18 °C, three measurements,

m = 0.06). The ACp used to correct to 25 °C was

estimated. Levi and Bisi report a value of 7,020

cal/mole for their dilute solution. Ishi’s value cor- rects to 6,780 ±100 cal/mole at 25 °C and infinite

dilution.

The dissociation pressure measurements of Riganti [641] lead to ambiguous results and cannot be

used as corroborating evidence for the difference,

AH° NaC102 (c) - AH° NaC102

• 3H2 0(c).

“Best”! value, A//° = 6,830 ± 100 cal/mole.

NaC103(c)

Ai/soin has been measured by Colomina and Nicolas [145] (1949; 25 °C, 14 measurements, m = 8.54

to 0.11), Nelson, Moss, and Hepler [551] (1960; 25

°C, six measurements, m = 0.02 to 0.01), and Ishi

[550] (1961; 18 °C, one measurement, m = 0.06).

The values of A are 5,191 ±10, 5,191 ±60, and

5,056 ±100 cal/mole, respectively.

Measurements have also been reported by Foote

and Saxton [552], Bronsted [553], and Berthelot

[377],

“Best” value, AH° =5,191 ± 10 cal/mole.

NaC104 (c) Measurements of A//soln have been made by

Smeets [395] (1933; 18 °C, two measurements,

m = 0.21), Askew et al., [499] (1934; 20 °C, two

measurements, m = 0.005), Lange and Martin [397]

(1937; 25 °C, one measurement, m = 0.12), Colomina

and Nicolas [145] (1949; 25 °C, 19 measurements,

m= 12.22 to 0.13), and Vorob’ev et al., [261] (1960;

25 °C, ?, m = 0.12). The ACp used to correct to 25

°C was estimated. Their values correct to: Smeets,

3,318 ±30; Askew et al., 3,340 ±20; Lange and

Martin, 3,429; Colomina and Nicolas, 3,317 ±8;

Vorob’ev et al., 3,329 ±20 cal/mole.

Other measurements have been reported by

Berthelot [216, 377].

“Best” value, AH° = 3,317 ± 8 cal/mole.

NaC104 H2 0(c)

AHsoln has been measured by Smeets [395] (1933;

18 °C, two measurements, m = 0.20). The ACp used to correct to 25 °C has been estimated. This

value corrects to 5,384 ± 50 cal/mole.

The dissociation pressure measurements of Markowitz and Boryta [642] lead to a AH for the reaction,

NaC104(c) ± H2 0(1) — NaC104

• H2 0(c), in fair agreement with the difference, AH° NaC104(c) —

A

H°

NaC104

• H2 0(c).

“Best” value, A//° = 5,380 ± 50 cal/mole.

NaBr(c)

A//soln has been measured by Thomsen [30] (1883;

17 and 20 °C, ?, 7/1 = 0.28), Chipman, Johnson, and

Maass [133] (1929; 25.4 °C, 15 measurements,

m= 1.42 to 0.11), Askew et al., [499] (1934; 20 °C, one measurement, 7/1 = 0.01), Wiist and Lange [21]

(1925; 25 °C, 15 measurements, //i = 8.63 to 1.02),

Lange and Durr [389] (1926; 25 °C, four measurements, m = 0.56), Slansky [399] (1940; 25 °C, own

extrapolation to infinite dilution), and Wallace [328]

(1949; 25 °C, six measurements, m = 0.06 to 0.03).

The values of AH° are: Thomsen, —87; Chipman

et al., — 45±200; Askew et al., —180; Wiist and

Lange, — 149 ± 15; Lange and Durr, —248; Slansky, — 40; Wallace, — 144 ± 15. Other measurements have been reported by

Berthelot [377], Favre and Valson [554], and Varet

[479].

“Best” value, AH° =— 144 ± 15 cal/mole.

NaBr • 2H2 0(c)

A//soln has been measured by Berthelot [377]

(1875; 11 °C, one measurement, m = 0.12), Thomsen

[30] (1883; 19 °C, two measurements, m = 0.19), and

Samoilov [408] (1952; 25 °C, one measurement,

m = 0.06). The values of A//* are: Berthelot,

4,150; Thomsen, 4,454 ±50; Samoilov, 4,572 cal/

mole. Favre and Valson [554] also report a measurement.

The dissociation pressure measurements of Dingemans [643] and Bell [644] lead to a AH for the reaction, NaBr(c) + 2H2 0(l) = NaBr • 2H2 0(c), in good

agreement with the difference, A//° NaBr(c) — AHI NaBr • 2H2 0(c).

“Best” value, A//° = 4,454 ± 50 cal/mole.

NaBr03(c)

A//soln has been measured by Spencer and Hepler

[484] (1960; 25 °C, six measurements, m = 0.02 to 0.01) and Boyd and Vaslow [522] (1962; 25 °C, three

measurements, m = 0.007 to 0.01). The values of

AHZ are: 6,430±60 and 6,350±100 cal/mole,

rpmrppti vpI v “Best” value, A//° = 6,430 ± 60 cal/mole.

Nal(c)

A//soln has been measured by Berthelot [377]

(1875; 11 °C, one measurement, m = 0.11), Thomsen

[30] (1882; 20.1 °C, two measurements, m = 0.28),

Pickering [515] (1888; 18 °C, one measurement,

m = 0.28), Varet [479] (1896; 16 °C, one measurement, tt/ = 0.50), Mosnier [526] (1897; 15 °C, one measurement, m = 0.07), Wiist and Lange [21] (1925;

25 °C, 14 measurements, m= 9.82 to 0.63), Askew

et al., [499] (1934; 20 °C, two measurements,

m — 0.02), and Mishchenko and Sukhotin [555] (1954;

25 °C, five measurements, /ft = 0.10 to 0.02). The

values of A//* are: Berthelot, — 1,800±200; Thomsen, — 1,406 ± 100; Pickering, —1,652; Varet, — 1,565; Mosnier, —1,721; Wiist and Lange, — 1,808 ±20; Askew et al., — 1,781 ± 30; Mishchenko

and Sukhotin, — 1,788±25 cal/mole.

“Best” value, AH° =- 1 ,800 ± 20 cal/mole.

27
Nal 2H2 0(c)

A//soin has been measured by Berthelot [377]

(1875; 11 °C, one measurement, ra = 0.11), Thomsen

[30] (1882; 19 °C, two measurements, m = 0.18) and

Samoilov [408] (1952; 25 °C, one measurement,

m = 0.06). The values of AH° are: Berthelot, 3,680;

Thomsen, 3,855 ±50; Samoilov, 4,184 cal/mole.

Favre and Valson [554] also report a measurement.

The dissociation pressure measurements of Dingemans [645] lead to a AH for the reaction, Nal(c)

+ 2H2 0(l) = NaI • 2H20(c), in excellent agreement

with the difference, A//°NaI(c) — A//°NaI • 2H20(c).

“Best” value, Ai/° = 3,855 ± 50 cal/mole.

NaI03(c)

AHsoi n has been measured by Spencer and Hepler

[484] (1960; 25 °C, four measurements, m = 0.01 to 0.004) and Shidlovskil and Valkina [556] (1961; 25

°C, three measurements, m = 0.06). The values of

AHZ are 4,820 ±60 and 4,890 ±60 cal/mole, re- spectively.

“Best” value, A//° = 4,850 ± 60 cal/mole.

NaI04(c)

Kapustinskil and Yatsimirskil [557] (1949; 25 °C, one measurement, ?) report a value of 8,910 cal

mole for AHsoln . Correction to infinite dilution is not possible.

“Best” value, A//soln = 8,910 cal/mole.

NaN02 (c)

AHso\ n has been measured by Swietoslawski [558]

(1910; 18 °C, one measurement, m = 0.16), Matignon

and Marchal [559] (1920; 20 °C, three measurements,

m = 0.16), Dode [306, 528] (1936; 12°C,two measurements, m = 0.13). Bureau [487] (1937; 20 °C, one measurement, m = 0.14), Perreu [149] (1941; 14 °C,

four measurements, 771 = 0.14), and Reshetnikov

[429] (1961; 25 °C, five measurements, m = 0.17).

The specific heat of the crystal used to correct to 25 °C was obtained from Voskresenskaya, Yankovskaya, and Anosov [621]. <£>/, has been assumed

to be 50 cal/mole at these concentrations. The

values of AHZ are: Swietoslawski, 3,300; Matignon

and Marchal, 3,300; Dode, 3,110; Bureau, 3,370;

Perreu, 3,300; Reshetnikov, 3,320 ± 70 cal/mole.

Reshetnikov’s value is obtained from the A//soln of a mechanical mixture of NaN02 with NaOH.

“Best” value, AJ/° = 3,320 ±40 cal/mole.

NaN03(c)

A//soln has been measured by Winkelmann [94]

(1873; 20 to 28 °C, 16 measurements, m = 2.79 to

0.37), Berthelot [377] (1875; 13 °C, one measurement, m = 0.74), Tilden [560] (1884; 16 °C, three

measurements, 777 = 0.56), Thomsen [30] (1883; 18

°C, three measurements, 771 = 0.28), von Stackelberg

[275] (1898; 17 °C, two measurements, m — 0.28 and

0.14), Haigh [388] (1912; 21 °C, three measurements,

tti = 0.14), Mondain-Monval [268] (1923; 16 °C, one measurement, 777 = 0.37), Voskresenskaya and Ponomareva [400] (1946; 25 °C, one measurement,

777 = 0.18), Lange and Martin [397] (1937; 25 °C, one

measurement, 777 = 0.12), and Van Tassel and Wendlandt [561] (1959; 25 °C, five measurements, m = 0.28). The values of A are: Winkelmann, 4,840

±150; Berthelot, 4,700; Tilden, 4,772; Thomsen,

4,904 ±50; von Stackelberg, 4,965 ±100; Haigh,

4,790; Mondain-Monval, 4,640; Voskresenskaya and

Ponomareva, 4,825; Lange and Martin, 4,892; Van

Tassel and Wendlandt, 4,980 ± 100 cal/mole. Measurements have also been reported by Scholz [316],

Varali-Thevenet [442], Mondain-Monval [276], and

Zawidzki and Schagger [562].

“Best” value, A//° = 4,900 ± 50 cal/mole.

NaC2H302 (c)

Ai/goin has been measured by Thomsen [30] (1883;

19 °C, two measurements, 777 = 0.28), Pickering

[384] (1887; 15 to 25 °C, 39 measurements, 777 = 0.28)

and Jolly [563, 564] (1952; 25 °C, three measurements, m = 0.008 to 0.005). The specific heat of

the crystal used to correct to 25 °C was obtained

from Strelkov [622]. The values of AH° are: Thomsen, —4,136 ±50; Pickering, —4,200 ±50;

and Jolly, — 4,144 ± 100 cal/mole.

AHsoin has also been measured by Berthelot [377,

476].

“Best” value, AH° = — 4,140 ± 50 cal/mole.

NaC2 H302

* 3H2 0(c)

Ai/soin has been measured by Thomsen [30] (1883;

19 °C, two measurements, 777 = 0.14), Pickering

[384] (1887; 15 to 25 °C, 33 measurements m, — 0.28),

Bindel [154] (1890; 21 °C, four measurements,

777 = 5.55 to 1.11), Calvet [250] (1933; 17 °C, three

measurements, 777 = 0.28), and Perreu [153] (1940; 18

°C, one measurement, m — 0.12). The values of AH°

are: Thomsen, 4,800 ±50; Pickering, 4,715 ±50;

Bindel, 4,534 ±75; Calvet, 4,682 ±75; Perreu,

4,663 ±100 cal/mole.

Other measurements have been reported by

Berthelot [476] and Gnesotto and Fabris [156].

The dissociation vapor pressure measurements of

Baxter and Cooper [6461 lead to a AH for the

reaction, NaC2H3 02(c) + 3H2 0(1) = NaC2 H302

• 3H2 0(c), in good agreement with the difference

A NaC2 H302(c) — A//° NaC2 H3 02

• 3H2 0(c).

“Best” value, A//° = 4,700 ± 75 cal/mole.

NaCN(c)

AHsoin has been measured by Joannis [496] (1882;

9 °C, three measurements, 777 = 0.56). The specific

heat of the solid used to correct to 25 °C was

obtained from Messer and Ziegler [623]. <bc was estimated. has been estimated as —30

cal/mole at 777 = 0.56. The value of AH°x is 290

cal/mole.

“Best” value, A//°=290 ± 200 cal/mole.

NaCN ^H2 0(c)

A//soi n has been measured by Joannis [496] (1882;

6 °C, one measurement, 777 = 0.56). <1>l has been

estimated as — 30 cal/mole at 777 = 0.56. The value,

recomputed to A//°, is 790 cal/mole.

“Best” value, A//° = 790 ±200 cal/mole.

28
NaCN 2H20(c)

A//soin has been measured by Joannis [496] (1882;

9 °C, three measurements ra = 0.56). <I>l has been

estimated as — 30 cal/mole at m — 0.56. The value

of AH°x is 4,440 cal/mole.

“Best” value, Af/° = 4,440 ± 200 cal/mole.

NaCNO(c)

AHsoUl has been measured by Lord and Woolf

[565] (1954; 25 °C, one measurement, m=0.03)

and Lemoult [566] (1899; 13 °C, four measurements, ra = 0.05 to 0.02). <£>l has been estimated

as 50 cal/mole at these concentrations. The values

of A//° are: 4,590 ±40 and 4,630 ± 100 cal/mole,

respectively.

“Best” value, A//° = 4,590 ± 40 cal/mole.

NaCNS(c)

AHso\ n has been measured by Vrzhesnevskii [448]

(1912; 18 °C, one measurement, m = 0.56) and Part- ington and Soper [334] (1929; 25 °C, 19 measurements, m— 1.23 to 0.17). The ACp used to correct

to 25 °C was estimated. The values of AH° are

1,670 and 1,632 ±20 cal/mole, respectively.

“Best” value, AH° — 1,632 ± 20 cal/mole.

KOH(c)

Ai/goin has been measured by Berthelot [307, 377]

(1875; 11.4 °C, one measurement, ra = 0.21), Thomsen [30] (1883; 18 °C, one measurement, m = 0.22),

de Forcrand [567] (1902; 21.5 °C, one measurement,

m = 0.33), Voskresenskaya and Ponomareva [400]

(1946; 25 °C, two measurements, /n = 0.18), and

Reshetnikov [429] (1961; 25 °C, six measurements,

m = 0.09). The values of AH° are: Berthelot, — 13,270; Thomsen, —13,750 ±100; de Forcrand, — 13,257; Voskresenskaya and Ponomareva,—7,660;

Reshetnikov, —13,769 ± 20 cal/mole.

“Best” value, AH° =— 13,769 ±20 cal/mole.

KOH nH2 0(c)

de Forcrand [567] (1902; 21.5 °C, one measure- ment for each composition, ra = 0.28) measured

AHsoin °f various compositions of KOH • nH2 0(c),

where n =0.25, 0.535, 0.91, 1.16, and 1.55. Berthelot’s [307] measurements (1875; 11.4 °C, one meas- urement for each composition, /n = 0.33) were

on compositions where n = 0.875 and 2. The AH°

values obtained were plotted, together with the

values of AHZ KOH(c) to obtain the AH° values

for the hydrates, KOH • H2 0(c) and KOH • 1.5H2 0(c).

Berthelot’s measurements on KOH • 2H2 0(c) appear to be seriously in error. No value for this is given.

The dissociation pressure measurements of Shibata, Oda, and Furukawa [650] and Bolte [651] are inconclusive.

KOH • H2 0(c). “Best” value, AH°=- 3,500 ± 300

cal/mole.

KOH • 1.5H2 0(c). “Best” value, AH° = - 2,500

± 300 cal/mole.

KF(c)

AHsoln has been measured by Guntz [187] (1884;

18 °C, one measurement, m = 0.28), de Forcrand

[335, 513] (1911; 15 °C, one measurement, ra = 0.50),

Lange and Eichler [338] (1927; 25 °C, eight measurements, m = 3.16 to 0.21), and Lange and Martin

[397] (1937; 25 °C, one measurement, ra = 0.31).

The values, recomputed to AH° are: Guntz, —3,950;

de Forcrand, —4,540; Lange and Eichler, —4,238

± 40 (standard deviation is ± 4); Lange and Martin, — 4,007 cal/mole.

“Best” value, AH° =—4,238 ±40 cal/mole.

KF 2H2 0(c)

AHsoln has been measured by Guntz [187] (1884;

20 °C, one measurement, m = 0.28), de Forcrand

[335, 513] (1911; 15 °C, one measurement, m = 0.50),

and Lange and Eichler [338] (1937; 25 °C, two measurements, m = 0.47 and 0.40). The values of AH°

are: Guntz, 830; de Forcrand, 1,890; Lange and

Eichler, 1,666 ±20 cal/mole.

The dissociation pressure measurements of Bell

[647] lead to a AH for the reaction, KF(c) + 2H2 0(c) = KF-2H2 0(c), in excellent agreement with the dif- ference A//^KF(c) — A//^KF-2H2 0(c). “Best” value, AH° = 1,666 ± 20 cal/mole.

KF 4H2 0(c)

de Forcrand’s reported value [335, 513] (1911;

15 °C, one measurement, m = 0.51) for A//soi n is 6,160 cal/mole. The melting point, reported by

Yatlov and Polyakov [635] is 17.5 °C. A hypothetical AH°x at 25 °C would be 6,080 ± 200 cal/mole.

KC103(c)

AHS0\ n has been measured by Berthelot [377]

(1875; 10 °C, one measurement, m = 0.18), Thomsen

[30] (1882; 19 °C, two measurements, m = 0.14), von Stackelberg [275] (1898; 16 °C, five measurements, m = 0.50 to 0.11) and Nelson, Moss, and

Hepler [551] (1960; 25 °C, six measurements,

m = 0.02 to 0.005). The values of AHZ are: Berthelot, 9,610; Thomsen, 9,916 ± 50; von Stackelberg, 10,000 ± 100; Nelson, Moss, and Hepler,

9,870 ± 50 cal/mole.

Bindel [154] has also reported a measurement.

“Best” value, AH°X = 9,890 ± 50 cal/mole.

KC104(c)

AHsoin has been measured by von Stackelberg

[275] (1898; 16 °C, four measurements, m = 0.22

to 0.06), Noyes and Sammet [568] (1903; 21 °C, seven measurements, m = 0.12), Latimer and Ahlberg [569] (1930; 25 °C, ?, m = 0.03), Birky and

Hepler [481] (1960; 25 °C, seven measurements,

ra = 0.009 to 0.004) and Vorob’ev et al., [261] (1960;

25 °C, ?, m = 0.01). The values of AH°x are: von

Stackelberg, 12,310 ±100; Noyes and Sammet,

12,154 ±30; Latimer and Ahlberg, 12,110 ±50;

Birky and Hepler, 12,300 ±60; Vorob'ev et al., 12,127 ±60 cal/mole.

29
Berthelot [215, 216] has also reported measurements.

“Best” value, A//^ = 12,200 ±60 cal/mole.

KBr(c)

AZ/soln has been measured by Thomsen [30] (1883;

19.6 °C, two measurements, m — 0.28), Bronsted

[385] (1906; 20 °C, eight measurements, m = 0.08),

Walden [500] (1907; 16.6 °C, two measurements,

/n = 0.28), Wiist and Lange [21] (1925; 25 °C, 31

measurements, ra = 5.25 to 0.37), Popov, Bundel,

and Choller [165] (1930; 20 °C, seven measurements,

m = 0.19), Chipman, Johnson, and Maass [133]

(1929; 15.8 to 27 °C, 30 measurements, m = 0A‘S to 0.09), Fedorov and Sil’chenko [271] (1933; 23.5 °C,

three measurements, m = 0.56 to 0.14), Lange and

Martin [397] (1937; 25 °C, one measurement,

m = 0.13), Popov, Skuratov, and Strel’tsova [172]

(1940; 20.5 °C, m = 0.12), and Hietala [426] (1960;

25 °C, three measurements, m = 0.28). The values

of AH° are: Thomsen, 4,769 ±50; Bronsted, 4,756

±50; Walden, 4,727 ±50; Popov, Bundel, and Choller, 4,685 ±50; Wiist and Lange, 4,777 ±40; Chipman, Johnson, and Maass, 4,753 ± 100; Federov and

Sil’chenko, 4,889 ±100; Lange and Martin, 4,783;

Popov, Skuratov, and Strel’tsova, 4,542; Hietala,

4,739 ± 20 cal/mole. Measurements have also been

reported by Scholz [316], Berthelot [348, 377], Berthelot and Ilosvay [383], and Balarew and Kolarow

[570]. Wiist and Lange’s measurements appear

to run high, as shown by their work on KC1. In

view of this and Hietala’s more recent measure- ments on KBr and KC1, a value of 4,750 ±20

cal/mole has been chosen.

“Best” value, AH° = 4,750 ± 20 cal/mole.

KBr03(c)

A//soln has been measured by Berthelot [216, 571]

(1878; 11 °C, one measurement, m — 0.12), Thomsen

[30] (1883; 19 °C, two measurements, m = 0.28), von Stackelberg [275] (1898; 16 °C, three measurements, m = 0.22 and 0.11), Lange and Martin [397]

(1937; 25 °C, one measurement, ra = 0.03), Mel,

Jolly, and Latimer [572, 573] (1953; 25 °C, three

measurements, m = 0.02 to 0.009), and Boyd and

Vaslow [522] (1962; 25 °C, one measurement,

m = 0.003). The values of AH° are: Thomsen,

9,832 ± 50; Berthelot, 9,300; von Stackelberg,

9,710 ± 100; Lange and Martin, 9,888; Mel, Jolly,

and Latimer, 9,780 ±30; Boyd and Vaslow, 9,700

± 100 cal/mole.

“Best” value, A//° = 9,830 ± 50 cal/mole.

KI(c)

AHsoln has been measured by Thomsen [30] (1882;

19 °C, two measurements, m = 0.28), Wiist and

Lange [21] (1925; 25 °C, 24 measurements, m — 7.95

to 0.29), Lange and Martin [397] (1937; 25 °C, one measurement, m = 0.11), Popov, Skuratov, and

Strel’tsova [172] (1940; 20.5 °C, one measurement,

m = 0.09), Bobtelsky and Lairsch [530] (J950; 24.5

°C, one measurement, m = 0.30), and Kapustinskil

and Drakin [411] (1952; 25 °C, one measurement,

m = 0.0008). The values of AH° are: Thomsen,

4,830 ±50; Wiist and Lange, 4,897 ±40 (standard

deviation is ±2); Lange and Martin, 4,873; Popov,

Skuratov, and Strel’tsova, 4,790 ± 100; Bobtelsky

and Lairsch, 5,020; Kapustinskil and Drakin, 4,830

±70 cal/mole. Measurements have also been re- ported by Berthelot [377], Berthelot and Ilosvay

[383], Scholz [316], Walden [500], Kantola [574], and

Hieber and Miihlbauer [575].

Wiist and Lange’s measurements tend to run

slightly high. In view of this, a value of 4,860 ± 30

cal/mole has been selected.

“Best” value, A//° = 4,860 ±30 cal/mole.

KI03 (c)

A//soi n has been measured by Berthelot [349]

(1878; 12 °C, one measurement, m = 0.12), Thomsen

[30] (1882; 19 °C, three measurements, ra = 0.13 to 0.10), von Stackelberg [275] (1898; 16 °C, four

measurements, m = 0.22 to 0.11), and Spencer and

Hepler [484] (1960; 25 °C, five measurements,

m = 0.01 to 0.006). The values of AHx are; Berthelot, 5,600; Thomsen, 6,640 ±50; von Stackelberg,

6,610 ± 100; Spencer and Hepler, 6,630 ± 50 cal/

mole.

“Best” value, A//° = 6,630 ±50 cal/mole.

KN02(c)

AHsoln has been measured by Dode [306, 528]

(1936; 12 °C, four measurements, ra = 0.14), Bureau

[487] (1937; 20 °C, one measurement, m = 0.14), and

Reshetnikov [429] (1961; 25 °C, three measurements,

m — 0.17). The ACp used to correct to 25 °C was

estimated. <IV has been estimated as —50 cal/mole

at the above concentrations. The values of AH°

are: Dode, 3,240 ± 150; Bureau, 3,270 ± 150;

Reshetnikov, 3,190 ±70 cal/mole. Reshetnikov’s

value is obtained from the A//soln of a mechanical

mixture of KOH with KN02 . “Best” value, A//° = 3,190 ±70 cal/mole.

KN03(c)

Values for AHx are shown in table XX. Other

measurements have been reported by Lloyd and

Wyatt [71], Scholz [316], Person [584], Hieber and

Miihlbauer [575], Varali-Thevenet [442], Staub [543],

Berthelot [225, 377], Anderson and Noyes [478],

Leval’t-Ezerskii [585], Graham [352], Colson [350],

and Zawidzki and Schagger [562].

Part of the discrepancy in the tabulated values

may be due to the presence of a few percent of the

metastable form.

“Best” value, AH°X — 8,340 ±30 cal/mole.

KC2 H3 02 (c)

A//soln has been measured by Thomsen [30] (1883;

19 °C, one measurement, ra = 0.28). The specific

heat of the crystal used to correct to 25°C was esti- mated. The value of AH°x is — 3,665 ± 50 cal/mole.

“Best” value, AHX =—3,665 ±50 cal/mole.

30
KCN(c)

Thomsen [30] (1883; 18 °C, two measurements,

m = 0.32) and Lange and Martin [397] (1937; 25 °C, one measurement, m = 0.32) have measured AHsoln . Messer and Ziegler [623] measured the specific heat

of the crystal. 3>c was estimated. <1>l has been

estimated to be 10 and 60 cal/mole, respectively, at the measured concentrations. The values of

A are 2,860 ±75 and 2,745 cal/mole, respectively.

Berthelot has also measured AHsoin [216, 586].

“Best” value, A//° = 2,800 ±100 cal/mole.

KCNO(c)

AHso\ n has been measured by Myers [203] (1958;

25 °C, four measurements, m = 0.01); Vanderzee

and Myers [204] report the same measurements.

O/. has been estimated as 40 cal/mole at /n = 0.01.

Their value of AH°X is 4,840 ±25 cal/mole.

Berthelot [495] also has measured AHsoin . “Best” value, AH°X = 4,840 ±25 cal/mole.

KCNS(c)

AHsoin has been measured by Joannis [496] (1882;

13 °C, three measurements, m = 0.28), Vrzhesnevskil [448] (1912; 18 °C, one measurement, m = 0.56),

and Partington and Soper [334] (1929; 25 °C, 14

measurements, m = 2.98 to 0.25). The specific heat

of the crystal used to correct to 25 °C was esti- mated. The values of AH°k

are: Joannis, 5,930;

Vrzhesnevskii, 6,090; Partington and Soper,

5,789 ±50 cal/mole.

“Best” value, AH°X = 5,790 ±50 cal/mole.

KMn04(c)

AZ/soin has been measured by Thomsen [30] (1883;

18 °C, two measurements, m = 0.11), Roth and

Becker [587] (1932; 16 to 21 °C, six measurements,

m = 0.08 to 0.01), Perreu [174] (1940; 18 °C, one measurement, ra = 0.05), and Nelson, Moss, and

Hepler [551] (1960; 25 °C, six measurements,

m = 0.01 to 0.005). The values of AH° are: Thomsen, 10,260 ±150; Roth and Becker, 10, 340 ±100;

Perreu, 10,180; Nelson, Moss, and Hepler, 10,410

±60 cal/mole.

“Best” value, A//; = 10,410 ±60 cal/mole.

RbOH(c)

A^soin has been measured by deForcrand [510]

(1906; 20 °C, one measurement, m = 0.50). The

specific heat of the crystal used to correct to 25 °C was estimated. 9>l has been estimated as 200

cal/mole at this concentration. The value of

A is —14,900 cal/mole.

“Best” value, AH°=— 14,900 ±200 cal/mole.

RbOH H2 0(c)

A//soin h&s been measured by de Forcrand [510]

(1906; 20 °C, one measurement, m = 0.50). has

been estimated as 200 cal/mole at this concentration.

The value of AH° is —4,310 cal/mole.

“Best” value, AH°= — 4,310 ±200 cal/mole.

RbOH 2H2 0(c)

AHsoin has been measured by de Forcrand [510]

(1909; 15 °C, one measurement, m = 0.50). has

been estimated as 200 cal/mole at this concentration.

The value of AH° is 210 cal/mole.

“Best” value, A//° = 210 ±200 cal/mole.

RbF(c)

de Forcrand [513, 588] (1911; 15 °C, one measurement, m = 0.50), measured AHsoln . The value of

AH° is —6,240 cal/mole.

“Best” value, A//°= — 6,240 ±200 cal/mole.

RbFH2 0(c)

de Forcrand [589] (1911; 15 °C, one measurement,

m = 0.50), measured A//soln of the substance with

the composition RbF-l/3H2 0. Lannung [648]

showed the existence of RbF-H2 0. The A

RbF(c) and the A for RbF l/3H2 0 were used to obtain AH° RbF*H2 0(c) =— 100 cal/mole.

“Best” value, AH°=— 100 ±300 cal/mole.

RbF l |H2 0(c)

de Forcrand [589] (1911; 15 °C, one measurement,

m = 0.50), measured A//soln . The value of AH°

is 320 cal/mole.

“Best” value, A//^ = 320±200 cal/mole.

RbCl(c)

AHsoin has been measured by de Forcrand [354]

(1906; 19 °C, one measurement, m = 0.25) and [513,

588] (1911; 15 °C, one measurement, m = 0.50),

Zemczuzny and Rambach [441] (1910; 18 °C, one measurement, m = 0.56), Haigh [388] (1912; 21 °C,

three measurements, /n = 0.14), Samoilov [590]

(1956; 25 °C, one measurement, m = 0.06), and

Samoilov and Buslaeva [444] (1960; 15 and 35 °C,

two measurements, m = 0.06). The values of

A//° are: de Forcrand, 4,028 and 4,100; Zemczuzny

and Rambach, 4,127; Haigh, 4,000 ±50; Samoilov,

4,112 ±50; Samoilov and Buslaeva, 4,151 ±75

cal/mole.

“Best” value, A//° = 4,130 ±75 cal/mole.

RbC103(c) AHsoin has been measured by Pitzer [591] (1938;

25 °C, two measurements, m = 0.01). has been

estimated as 25 cal/mole at this concentration.

The value of A//° is 11,410 ± 60 cal/mole.

“Best” value, A//°= 11,410 ±60 cal/mole.

RbC104 (c)

A//soln has been measured by Pitzer [591] (1938;

25 °C, two measurements, ra = 0.01). has been

estimated as 10 cal/mole at this concentration.

The value of AH°x is 13,565 ±60 cal/mole.

“Best” value, A//° = 13,560 ±60 cal/mole.

RbBr(c)

A//soin has been measured by de Forcrand [513,

588] (1911; 15 °C, one measurement, m = 0.50) and

Lange and Martin [397] (1937; 25 °C, one measure31
ment, m = 0.11). The values of A//° are 5,618 and

5,230 cal/mole, respectively.

“Best” value, A//; - 5,230 ±100 cal/mole.

RbBr03(c)

A#soin has been measured by Boyd and Vaslow

[5221 (1962; 25 °C, three measurements, m = 0.004).

has been estimated to be 20 cal/mole at this

concentration. The value of AH° is 11,700 ± 100

cal/mole.

“Best” value, A#° = 11,700 ± 100 cal/mole.

Rbl(c)

A//soln has been measured by Mosnier [526] (1897;

15 °C, one measurement, m = 0.06) and de Forcrand

[513, 588] (1911; 15 °C, one measurement, ra = 0.50).

The values of AH° are 5,675 and 6,225 cal/mole,

respectively.

“Best” value, AH° = 6,000 ± 300 cal/mole.

RbN03(c)

A//soln has been measured by Haigh [388] (1912;

21 °C, three measurements, ra = 0.14) and Vorobiev,

Skuratov, and Ebragen [592] (1961; ?, ?, ra = 0.03).

The specific heat of the crystal used to correct to 25 °C was obtained from Mustajoki [624]. Haigh’s

value corrects to 8,716 ±60 cal/mole at 25 °C and

infinite dilution. Vorobiev’s reported value of 8,910

for AHsoln is a preliminary one; hence it is given little weight in the selection of AH°.

“Best” value, AH° — 8,720 ±60 cal mole.

CsOH(c)

Ai/soln has been measured by Beketov [593] (1892;

16 °C, one measurement, m = 0.17) and de Forcrand

[510] (1906; 15 °C, one measurement, m = 0.50).

The specific heat of the solid used to correct to 25 °C was estimated. <!>/, has been estimated as 160

and 230 cal/mole, respectively, at the measured concentrations. The value of AH°x are —16,470 and

—17,090 ±200 cal/mole, respectively.

“Best” value, A//° =—17,100 ±200 cal/mole.

CsOH H2 0(c)

A//soln has been measured by de Forcrand [510]

(1906; 15 °C, one measurement, m = 0.50).

has been estimated as 230 cal/mole at this concentration. The value of AH°x

is —4,900 ±200 cal/mole.

“Best” value, A//° = —4,900 ±200 cal/mole.

CsF(c)

A//soln has been measured by de Forcrand [513,

588] (1911; 15 °C, one measurement, m = 0.50).

The value of AH°x is —8,810 ±200 cal/mole.

“Best” value, AH°X = — 8,810 ± 200 cal/mole.

CsF • H2 0(c)

de Forcrand [589] (1911; 15 °C, one measurement,

m = 0.50) measured AHsoin of the substance with

the composition CsF • 2/3H2 0. Lannung [648]

showed the existence of CsF • H2 0(c). AH°x CsF

and A//° for CsF • 2/3H2 0 were used to obtain

AH°x of CsF • H2 0=—2,500 cal/mole.

“Best” value, A//° =— 2,500 ± 300 cal/mole.

CsF li H2 0(c)

de Forcrand [589] (1911; 15 °C, one measurement,

m = 0.50) has measured A//soln . The value of AH°

is — 1,300 cal/mole.

“Best” value, AH°=— 1,300 ± 200 cal/mole.

CsCl(c)

A//soln has been measured by de Forcrand [354]

(1906; 19 °C, one measurement, m = 0.25) and [513,

588] (1911; 15 °C, one measurement, m = 0.50),

Haigh [388] (1912; 21 °C, three measurements,,

m = 0.14), Samoilov [5901 (I960; 25 °C, one measurement, m = 0.05), Rodnikova [594] (1958; 15 and 35

°C, six measurements, m = 0.05), and Samoilov and

Buslaeva [444] (1960; 15 and 35 °C, three measurements, m = 0.06). The values of AH° are: de

Forcrand, 4,300 and 4,320; Haigh, 4,077 ±50;

Samoilov, 4,254; Rodnikova, 4,180 ± 100; Samoilov

and Buslaeva, 4,180 ± 100 cal/mole.

Beketov and Beketov [527] also measured A//soln , using mechanical mixtures of CsCl with Lil, Nal,

and KI.

“Best” value, A//° = 4,250 ± 100 cal/mole.

CsClO-dc)

Pitzer [591] (1938; 25 °C, four measurements,

m — 0.002 to 0.009) has measured AHsoln . <t> L has

been estimated as 15 cal/mole in this concentration

range. The value of AH°x is 13,250 ± 100 cal/mole.

“Best” value, AH° = 13,250 ± 100 cal/mole.

CsBr(c)

AHsoln has been measured by de Forcrand [513,

588] (1911; 15 °C, one measurement, m = 0.50) and

Lange and Martin [397] (1937; 25 °C, one measurement, m = 0.11). The values of A//° are 6,420 and

6,210 cal/mole, respectively.

“Best” value, AH° = 6,210 ± 100 cal/mole.

CsBr03 (c)

AHsoln has been measured by Boyd and Vaslow

[522] (1962; 25 °C, five measurements, m — 0.005 to 0.001). has been estimated as 20 cal/mole in

this concentration range. The value of A//° is 12,060 ± 100 cal/mole.

“Best” value, A = 12,060 ± 100 cal/mole.

Csl(c)

A//soln has been measured by Beketov and

Beketov [527] (1904; 18 °C, three measurements,

m = 0.16 to 0.12) and de Forcrand [513, 588] (1911;

15 °C, one measurement, m = 0.50). Beketov and

Beketov’s measurements were with mechanical

mixtures of Csl with LiCl, NaCl, and KC1. The

values of A//° are 7, 960 ±150 cal/mole and 7,970

cal/mole, respectively.

“Best” value, A//° = 7,970 ± 100 cal/mole.

32
CsN03(c)

A//soin has been measured by Haigh [388] (1912;

21 °C, four measurements, 777 = 0.14). The value

of AH°x is 9,560 ±50 cal/mole.

“Best” value, A//° = 9,560 ± 50 cal/mole.

VIII. Review Papers

Besides those mentioned in the introduction, there

are numerous review and compilation papers on the

thermal properties of the aqueous uni-univalent

electrolytes. Among these are Eigen and Wicke

[625], Latimer [626], Mishchenko [627], Gucker [628],

Wiist and Lange [629], Vasil’ev et al. [630], Robinson

and Frank [631], and Kapustinskil, Drakin and

Yakushevskil [632]. Particular note should be

made of Robinson and Stoke’s [633] correlation of

activity coefficients, conductivities, osmotic coefficients, etc. No attempt is made here to list all review papers on the thermal properties of specific aqueous uniunivalent electrolytes. The following lists some for

the more important compounds.

HF

Elmore, Hatfield, Mason, and Jones [197] have

calculated the thermal properties at 25 °C. They

include the activity, free energy, enthalpy, entropy,

and molal heat capacity. Franck and Spalthoff

[611] correlate the specific heat at constant volume

with the density and temperature.

HC1

Van Nuys [596] presents charts summarizing the

enthalpy and heat of dilution data from 0 to 100 °C.

hno3 Chedin [597] reviews the properties of aqueous

HN03 , its hydrates, equilibrium equations, and

ionization. McCurdy and McKinley [598] correlate

the enthalpy-temperature data for the HN03-H2 S04-

H2 0 system. Kharbanda [619] provides a mono- gram which permits the calculation of the specific

heat of aqueous solutions from —40 to 192 °C.

Bump and Sibbitt [620] correlate the specific heat

data of aqueous mixtures of HN03 and H2SO4.

C2H4O2

Lemlich, Gottschlich, and Hoke [595] give an

enthalpy-concentration chart for acetic acid-water

mixtures.

NH3 Rozenfel’d [599] gives a temperature-entropy

diagram for the aqueous system.

nh4 no3 Othmer and Frohlich [600] construct an enthalpyconcentration diagram.

AgNOa

Kangro and Groeneveld [601], using vapor pres- sure data at 20 and 25 °C, calculate values of Li at 22.5

°C and the activity coefficients at 25 °C from

m = 15 to 1. LiOH

Kangro and Groeneveld [601], using vapor pres- sure data at 20 and 25 °C, calculate values of L\ at

22.5

°C and the activity coefficients at 25 °C from

/ra = 5 to 1. LiCl

Kangro and Groeneveld [601], using vapor pres- sure data at 20 and 25 °C, calculate values of J_ x at

22.5

°C and the activity coefficients at 25 °C from

777 = 18 to 1. LiBr

Lower [602] and Rozenfel’d and Karnaukh [603]

give isotherms for the enthalpy-concentration of

aqueous solutions.

LiNOs

Kangro and Groeneveld [601], using vapor pres- sure data at 20 and 25 °C, calculate values of Li at

22.5

°C and the activity coefficients at 25 °C from

777 = 20 to 1. NaOH

Rant [604, 605] gives diagrams for the enthalpyentropy-concentration-temperature properties.

Ginzburg [606, 610] gives the thermal properties of

concentrated solutions. Haltenberger [607] gives an enthalpy-concentration chart. Kangro and

Groeneveld [601], using vapor pressure data at 20

and 25 °C, calculate values of U at 22.5 °C and

the activity coefficients at 25 °C from 777 = 27 to 2. NaCl

Fabry [608] constructs a temperature-enthalpyconcentration chart. Shields [609] reviews the

physical and thermal properties of brine solutions.

NaNOg

Kangro and Groeneveld [601], using vapor pres- sure data at 20 and 25 °C, calculate values of L\

at 22.5 °C and the activity coefficients at 25 °C

from 777 = 9 to 1. KOH

Kangro and Groeneveld [601], using vsqjor pres- sure data at 20 and 25 °C, calculate values of L\

at 22.5 °C and the activity coefficients at 25 °C

from 777 = 21 to 1. kno3 Kangro and Groeneveld [601], using vapor pres- sure data at 20 and 25 °C, calculate values of L\

at 22.5 °C and the activity coefficients at 25 °C

from 777 = 3 to 1.

33
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(1929). [614] von Stackelberg, E„ Z. physik. Chem. 20, 159-167 (1896). [615] Seidell, A., Solubilities of inorganic and metal organic

compounds, Vol. I, 3d edition (D. Van Nostrand Co.,

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organic compounds, 3d edition, supplement (D. Van

Nostrand Co., Inc., New York, 1952). [617] Linke, W. F., Solubilities of inorganic and metal organic

compounds, Vol. I, 4th edition (D. Van Nostrand Co.,

Tnr- Npw York 19581

[618] Rossini, F. D„ Pitzer, K. S., Arnett, R. L„ Braun, R. M„

Pimentel, G. C., Li, K., Ries, H. J., Cowie, P. A., Mitchell,

J. , Parcella, L. A., Epstein, M. B., McClellan, A. L., Sarao, M. H., De Celles, C. R., and Flanagan, H. M.,

Selected values of physical and thermodynamic properties of hydrocarbons and related compounds (Carnegie

Press, Pittsburgh, Pennsylvania, 1953). [619] Kharbanda, O. P., Ind. Chemist 33, 136 (1957). [620] Bump, T. R., and Sibbitt, W. L., Ind. Eng. Chem. 47,

1665-1670 (1955). [621] Voskresenskaya, N. K., Yankovskaya, G. N., and Anosov,

V. Ya., Zhur. Priklad. Khim. 21, 18-25 (1948). [622] Strelkov, I. I., Ukrain. Khim. Zhur. 21, 551-553 (1955). [623] Messer, C. E., and Ziegler, W. T., J. Am. Chem. Soc. 63,

2703-2708 (1941). [624] Mustajoki, A., Ann. Acad. Sci. Fennicae, AVI, No. 9, 16 pp.

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(1954). [626] Latimer, W. M., Chem. Revs. 18, 349—358 (1936). [627] Mishchenko, K. P., Zhur. Fiz. Khim. 26, 1736-1760 (1952). [628] Gucker, F. T„ Jr., Ann. N.Y. Acad. Sci. 51, 680-704 (1949). [629] Wiist, J., and Lange, E., Z. Elektrochem. 30, 523-528

(1924). [630] Vasil’ev, V. P., Zolotarev, E. K., Kapustinskii, A. F., Mishchenko, K. P., Podgornaya, E. A., and Yatsimirskii, K. B„ Zhur. Fiz. Khim. 34, 1763-1767 (1960). [631] Robinson, A. L., and Frank, H. S., J. Am. Chem. Soc. 56,

2312-2313 (1934).

40
[632] Kapustinskil, A. F., Drakin, S. I., and Yakushevskii, B. M., Zhur. Fiz. Khim. 27, 433-442 (1953). [633] Robinson, R. A., and Stokes, R. H., Electrolyte solutions,

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2738-2741 (1951). [635] Yatlov, V. S., and Polyakov, E. M., Zhur. Obshchel Khim.

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1600 (1956).

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[648] Lannung, A., Z. physik. Chem. A170, 134^138 (1934). [649] Osborne, N. S., Stimson, H. F., and Ginnings, D. C., J. Research Natl. Bur. Standards 23, 197-260 (1939). [650] Shibata, F. L. E., Oda, S., and Furukawa, S., J. Sci. Hiroshima Univ. Ser. A2, 85-102 (1932). [651] Bolte, H., Z. physik. Chem. 80, 338—360 (1912). [652] Vanderzee, C. E., and Nutter, J. D., J. Phys. Chem. 67,

2521-2525 (1963).

X. Tables

Table 1

<l>®, cal/deg mole, of the ions at 25 °C

Ion <D

Oc

H+ NH4 +

.... Ag+ Li + Na+ K+ Rb+ Cs + OHFciC103-.... CIO4-.... Br- Br03 -... I-103

-

104-

no2 - no3 -.... CNS-.... cho2 -... c2 h3o2 - c3 h5 o2 - Mn04 -...

0

19.1 5.2 16.4

11.1

5.2 *3.3

1.9 -35.5

-25.5

-32.6

-19.7

-18.2

-33.9

-26.5

-34.0

-29.6 *- 28.2 -23.3

-20.7

-9.6 - 21.0 -1.5

+ 26.7 -19.6

*Estimated.

41
Table II A. Heat capacity: aqueous HCl

<I>c, cal/deg mole

Table II B. Heat capacity: aqueous NaOH

3>c» cal/deg mole

n m 15° 20° 25° 30° n m 15° 20° 25° 30°

00 0.00 - 34.8 - 33.8 - 32.6 - 31.9 00 0.00 - 34.4 - 29.4 - 24.4 - 18.9 100,000 .000555 - 34.6 - 33.6 - 32.4 - 31.7 100,000 .000555 - 34.3 - 29.3 - 24.3 - 18.8 50,000 .00111 - 34.6 - 33.6 - 32.4 - 31.6 50,000 .00111 - 34.3 - 29.2 - 24.2 - 18.7 20,000 .00278 - 34.5 - 33.5 - 32.3 - 31.5 20,000 .00278 - 34.2 - 29.1 - 24.1 - 18.6 10,000 .00555 - 34.4 - 33.3 - 32.2 - 31.4 10,000 .00555 - 34.1 - 29.0 - 23.9 - 18.5 7,000 .00793 - 34.3 - 33.2 - 32.1 - 31.3 7,000 .00793 - 34.0 - 28.9 - 23.8 - 18.4

5,000 .OHIO - 34.2 - 33.1 - 32.0 - 31.2 5,000 .OHIO - 33.8 - 28.7 - 23.7 - 18.3 4,000 .01388 - 34.2 - 33.1 - 31.9 - 31.1 4,000 .01388 - 33.7 - 28.6 - 23.6 - 18.2 3,000 .01850 - 34.1 - 33.0 - 31.8 - 31.0 3,000 .01850 - 33.5 - 28.4 - 23.4 - 18.0 2,000 .02775 - 33.9 - 32.8 - 31.6 - 30.8 2,000 .02775 - 33.2 - 28.1 - 23.1 - 17.8 1,500 .03700 - 33.7 - 32.6 - 31.4 - 30.6 1,500 .03700 - 32.8 - 27.7 - 22.8 - 17.2

1,000 .05551 - 33.4 - 32.3 - 31.2 - 30.3 1,000 .05551 - 32.1 - 27.1 - 22.2 - 17.2 900 .0617 - 33.3 - 32.2 - 31.2 - 30.3 900 .0617 - 31.9 - 26.9 - 22.0 - 17.0 800 .0694 - 33.2 - 32.1 - 31.1 - 30.2 800 .0694 - 31.6 - 26.6 - 21.8 - 16.9 700 .0793 - 33.1 - 31.9 - 30.9 - 30.0 700 .0793 - 31.3 - 26.3 - 21.5 - 16.7 600 .0925 - 32.9 - 31.8 - 30.8 - 29.9 600 .0925 - 30.8 - 25.9 - 21.2 - 16.4

500 .1110 - 32.7 - 31.6 - 30.6 - 29.7 500 .1110 - 30.2 - 25.4 - 20.7 - 16.1 400 .1388 - 32.4 - 31.3 - 30.3 - 29.5 400 .1388 - 29.4 - 24.6 - 20.0 - 15.5 300 .1850 - 31.9 - 30.9 - 30.0 - 29.1 300 .1850 - 28.1 - 23.5 - 18.9 - 14.6 200 .2775 - 31.1 - 30.2 - 29.3 - 28.5 200 .2775 - 25.8 - 21.4 - 17.1 - 13.1 150 .3700 - 30.4 - 29.6 - 28.8 - 27.9 150 .3700 - 23.8 - 19.7 - 15.5 - 11.8

100 .5551 - 29.3 - 28.6 - 27.8 - 27.1 100 .5551 - 20.4 - 16.6 - 12.9 -9.7 75 .7401 - 28.4 - 27.8 - 27.0 - 26.3 75 .7401 - 17.3 - 14.0 - 10.7 - 7.8 50 1.1101 - 27.0 - 26.4 - 25.6 - 25.1 50 1.1101 - 12.5 - 9.7 - 7.1 - 4.7 40 1.3877 - 26.1 - 25.5 - 24.8 - 24.3 40 1.3877 - 9.8 - 7.1 - 4.8 - 2.8 30 1.8502 - 24.7 - 24.2 - 23.6 - 23.2 30 1.8502 - 6.0 - 3.5 - 1.7 - 0.1

25 2.2202 - 23.7 - 23.2 - 22.7 - 22.3 25 2.2202 - 3.5 - 1.2 + 0.4 + 1.7 20 2.7753 - 22.4 - 21.9 - 21.5 - 21.2 20 2.7753 - 0.3 + 1.8 3.2 4.7 15 3.7004 — 20,5 - 20.2 - 19.8 —19.6 15 3.7004 + 4.1 5.7 6.8 7.7 12 4.6255 -. 18.8 - 18.5 - 18.2 - 18.0 12 4.6255 7.5 8.8 9.8 10.5 10 5.5506 - 17.3 - 17.0 - 16.8 - 16.6 10 5.5506 10.3 11.3 12.2 12.9

9.5 5.8427 - 16.8 - 16.6 - 16.4 - 16.2 9.5 5.8427 11.0 12.0 12.8 13.6

9.0 6.1674 - 16.4 - 16.1 - 15.8 - 15.7 9.0 6.1674 11.8 12.7 13.5 14.3

8.5 6.5301 - 15.8 - 15.6 - 15.4 - 15.2 8.5 6.5301 12.6 13.5 14.3 15.1 8.0 6.9383 - 15.3 - 15.1 - 14.8 - 14.6 8.0 6.9383 13.4 14.3 15.1 15.8

7.5 7.4008 - 14.7 - 14.5 - 14.2 - 14.0 7.5 7.4008 14.2 15.1 15.8 16.6

7.0 7.9295 - 14.0 - 13.8 - 13.5 - 13.2 7.0 7.9295 15.1 16.0 16.6 17.4

6.5 8.5394 - 13.2 - 13.0 - 12.7 - 12.5 6.5 8.5394 15.9 16.9 17.5 18.2

6.0 9.2510 - 12.3 - 12.1 - 11.8 - 11.6 6.0 9.2510 16.8 17.7 18.4 19.0

5.5 10.0920 - 11.3 - 11.1 - 10.8 - 10.6 5.5 10.0920 17.6 18.4 19.1 19.7

5.0 11.1012 - 10.1 - 9.8 - 9.6 - 9.4 5.0 11.1012 18.4 19.2 19.8 20.4

4.5 12.3346 - 8.2 - 8.5 - 8.7 - 8.0 4.5 12.3346 19.4 20.0 20.6 21.1

4.0 13.8765 - 7.1 - 6.8 - 6.6 - 6.5 4.0 13.8765 20.3 20.9 21.3 21.8

3.5 15.8589 - 5.1 - 4.9 - 4.7 - 4.6 3.5 15.8589 21.4 21.7 22.0 22.3

3.25 17.0788 21.8 22.0 22.2 22.5

3.0 18.5020 22.0 22.2 22.3 22.5

2.5 22.2024 22.0 22.1 22.2 22.3

2.0 27.7530 21.2 21.2 21.2 21.2

42
Table II C. Heat capacity: aqueous NaCl

<I>C, cal/deg mole

n m 15° 20° 25°

CoO

o

00 0.00 - 25.2 - 23.3 - 21.5 - 20.1 100,000 .000555 - 25.1 - 23.2 - 21.4 - 20.0 50,000 .00111 - 25.0 - 23.1 - 21.3 - 19.9

20,000 .00278 - 24.9 - 23.0 - 21.2 - 19.8 10,000 .00555 - 24.8 - 22.9 - 21.1 - 19.6 7,000 .00793 - 24.7 - 22.8 - 21.0 - 19.5 5,000 .OHIO - 24.6 - 22.7 - 20.9 - 19.4 4,000 .01388 - 24.5 - 22.6 - 20.8 - 19.3

3,000 .01850 - 24.4 - 22.5 - 20.7 - 19.2 2,000 .02775 - 24.2 - 22.3 - 20.4 - 19.0 1,500 .03700 - 23.9 - 22.0 - 20.2 - 18.8 1,000 .05551 - 23.4 - 21.6 - 19.8 - 18.4 900 .0617 - 23.3 - 21.4 - 19.6 - 18.2

800 .0694 - 23.1 - 21.3 - 19.5 - 18.1 700 .0793 - 22.8 - 21.0 - 19.3 - 17.9 600 .0925 - 22.5 - 20.8 - 19.0 - 17.6 500 .1110 - 22.0 - 20.3 - 18.6 - 17.3 400 .1388 - 21.4 - 19.8 - 18.2 - 16.9

300 .1850 - 20.5 - 19.0 - 17.5 - 16.2 200 .2775 - 19.0 - 17.5 - 16.3 - 15.1 150 .3700 - 17.7 - 16.4 - 15.2 - 14.1 100 .5551 - 15.5 - 14.8 - 13.4 - 12.5 75 .7401 - 13.6 - 12.6 - 11.7 - 10.9

50 1.1101 - 10.4 - 9.6 - 8.8 - 8.2 40 1.3877 - 8.3 - 7.6 - 7.0 - 6.4 30 1.8502 - 5.7 - 5.1 - 4.6 - 4.1 25 2.2202 - 3.5 - 2.9 - 2.4 - 2.0 20 2.7753 - 0.8 - 0.4 0.0 + 0.2

15 3.7004 + 3.3 3.5

12 4.6255 6.3 10 5.5506 9.0

9.5 5.8427 9.7 9.0 6.1674 10.5

43
Table III. Heat capacity: acids

<JV, cal/deg mole, at 25 °C

n m HF HC1 HBr HI hio3 HNOs ch2 o2 c2 h4 o2 C3H6O2

00 0.00 -25.5 -32.6 -33.9 -34.0 -29.6 -20.7 -21.0 -1.5 + 26.7 500,000 .000111 -23.0 -9.8 + 25.8 38 0 100,000 .000555 -18.8 -32.4 -33.8 -33.9 -29.4 -20.6 -1.2 32.6 45.1 50,000 .00111 -16.6 -32.4 -33.7 -33.8 -29.3 -20.5 + 3.1 34.0 48.3 20,000 .00278 -12.4 -32.3 -33.6 -33.7 -29.1 -20.4 10.2 35.7 52.2 10,000 .00555 -8.6 -32.2 -33.4 -33.5 -28.5 -20.3 12.7 36.9 54.1

7,000 .00793 -6.7 -32.1 -33.4 -33.4 -28.4 -20.2 13.7 37.4 54.8 5,000 .OHIO -4.9 -32.0 -33.3 -33.3 -28.1 -20.1 14.3 37.8 55.3 4,000 .01388 -3.6 -31.9 -33.2 -33.2 -27.7 -20.1 14.7 37.9 55.6 3,000 .01850 -2.2 -31.8 -33.1 -33.1 -27.2 -20.0 15.1 38.1 56.1 2,000 .02775 -0.5 -31.6 -32.9 -32.9 -25.8 -19.8 15.8 38.5 56.7

1,500 .03700 + 0.4 -31.4 -32.7 -32.7 -24.9 -19.6 16.4 38.7 57.1 1,000 .05551 1.6 -31.2 -32.5 -32.5 -23.0 -19.3 16.8 39.0 57.7 900 .0617 1.8 -31.2 -32.4 -32.4 -22.3 -19.2 17.0 39.0 57.8 800 .0694 2.0 -31.1 -32.3 -32.3 -21.5 -19.1 17.2 39.1 57.9 700 .0793 2.2 -30.9 -32.2 -32.1 -20.2 -19.0 17.3 39.2 58.0

600 .0925 2.4 -30.8 -32.1 -32.0 -18.7 -18.9 17.5 39.3 58.3 500 .1110 2.7 -30.6 -31.9 -31.7 -16.7 -18.7 17.7 39.4 58.4 400 .1388 2.8 -30.3 -31.6 -31.4 -13.9 -18.4 18.0 39.4 58.6 300 .1850 3.2 -30.0 -31.2 -30.9 -10.1 -17.9 18.3 39.4 58.8 200 .2775 3.3 -29.3 -30.6 -30.2 -4.7 -17.2 18.7 39.3 58.9

150 .3700 3.5 -28.8 -30.1 -29.6 -0.7 -16.4 18.9 39.2 58.8 100 .5551 3.8 -27.8 -29.1 -28.4 + 4.8 -15.0 19.0 39.1 58.7

75 .7401 4.1 -27.0 -28.5 -27.5 9.2 -13.7 19.2 38.9 58.6 50 1.1101 4.5 -25.6 -26.8 -25.9 15.7 -11.5 19.8 38.6 58.3 40 1.3877 4.9 -24.8 -25.9 -24.8 19.0 -9.9 19.8 38.4 58.0

30 1.8502 5.3 -23.6 -24.5 -23.3 23.1 -7.3 20.0 38.0 57.1 25 2.2202 5.6 -22.7 -23.6 -22.2 25.7 -5.4 20.1 37.7 56.2 20 2.7753 5.7 -21.5 -22.2 -20.8 -2.7 20.2 37.1 55.0

15 3 7004 6 0 — 19 8 — 20 3 + 14 20.4 36.3 53 1 12 4.6255 6.2 — 18.2 — 18.5 5.0 20.4 35.4 51.3

10 5.5506 6.3 - 16.8 - 16.8 8 5 20.6 34.8 49.7

9.5 5.8427 6.4 — 16.4 — 16.3 9 2 20.6 34.7 9 0 6 1674 6 4 — 15 8 - 15 7 10 3 20.6 34.5

8.5 6.5301 6.5 - 15.4 - 15.1 11 4 20.7 34.4

8.0 6.9383 6.6 — 14.8 — 14.4 12.5 20.7 34.2

7.5 7.4008 6.7 - 14.2 -13.2 13 7 20.8 34.0

7.0 7.9295 6.9 - 13.5 - 12.7 14 9 20.8 33.8

6.5 8.5394 7.0 — 12.7 — 11.9 16 1 20.8 33.5

6.0 9.2510 7.1 - 11.8 - 10.8 17 1 20.9 33.3

5.5 10.0920 7.2 — 10.8 -9.6 18 3 20.9 33.0

5.0 11.1012 7.3 -9.6 -8.2 19 3 21.0 32.8

4.5 12.3346 7.4 -8.7 -6.8 20 4 21.1 32.5

4.0 13.8765 7.5 -6.6 -5.5 21 3 21.2 32.2

3.5 15.8589 7.6 -4.7 -4.0 22 1 21.3 31.8

3.25 17.0788 7.6 -3.2 22 6 21.4 31.7

3.0 18.5020 7.7 -2.3 23 0 21.5 31.5

2.5 22.2024 7.8 -0.4 23 8 21.6 31.2

2.0 27.7530 7.9 24 6 21.7 30.8

1.5 37.0040 25 2 21.8 30.4

1.0 55.506 25.7 22.0 30.1

44
Table IV. Heat capacity: ammonium and alkyl ammonium compounds

<I>C, cal/deg mole, at 25 °C

n m nh4 oh NH4F NH4CI NH4 Br* nh4 i* nh4 no3 CH3NH3CI (CH3)2NH2 C1 (CH3) 3 NHC1

00 0.00 -16.4 -6.4 -13.5 -14.8 -14.9 -1.6

500 000 .000111 + 19.4 100^000 .000555 26.7 -6.3 -13.4 (-14.7) (-14.8) -1.5

50,000 .00111 29.3 -6.2 -13.3 (-14.6) (-14.7) -1.4

20,000 .00278 31.5 -6.1 -13.2 (-14.5) (- 14.6) -1.3

10,000 .00555 32.7 -6.0 -13.1 (- 14.4) (- 14.5) -1.1

7,000 .00793 33.3 -5.9 -13.0 (-14.3) (-14.4) -1.0

5,000 .OHIO 33.6 -5.8 - 12.9 (-14.2) (-14.3) -0.9

4,000 .01388 33.7 -5.7 -12.8 (- 14.1) (- 14.2) -0.8

3,000 .01850 33.7 -5.6 -12.7 (- 14.0) (- 14.1) -0.7

2,000 .02775 33.7 -5.4 -12.6 (-13.9) (-14.0) -0.5

1,500 .03700 33.8 -5.2 -12.4 (-13.7) (-13.8) -0.2

1,000 .05551 33.9 -5.0 -12.1 (- 13.4) (-13.5) + 0.2 900 .0617 33.9 -4.9 -12.0 (-13.3) (-13.4) 0.4 800 .0694 34.0 -4.8 -11.9 (-13.2) (-13.3) 0.5 700 .0793 34.1 -4.7 -11.8 (-13.2) (-13.2) 0.8

600 .0925 34.1 -4.5 -11.7 (-13.0) (-13.0) 1.0 4.5 8.7 10.3 500 .1110 34.2 -4.4 -11.6 (-12.8) (-12.8) 1.3 5.1 9.6 11.2 400 .1388 34.4 -4.1 -11.3 (-12.5) (-12.4) 1.8 5.8 10.9 12.5 300 .1850 34.6 -3.6 -11.0 (-12.1) (-11.9) 2.5 6.7 12.7 14.3 200 .2775 34.8 -2.9 -10.3 (-11.4) (-10.9) 3.7 7.8 15.4 17.1

150 .3700 34.9 -2.3 -9.7 (-10.9) (-10.1) 4.8 8.2 17.2 19.3 100 .5551 35.2 -1.4 -8.7 (-9.8) (-8.7) 6.6 8.1 18.8 22.4

75 .7401 35.4 -0.6 -7.8 (-9.0) (-7.5) 8.0 7.5 19.4 24.5 50 1.1101 35.6 + 0.7 -6.2 (-7.5) (-5.5) 10.4 5.6 19.4 26.8 40 1.3877 35.7 1.7 -5.3 (-6.5) (-4.3) 11.9

30 1.8502 35.7 2.8 -3.9 (-5.0) (-2.5) 14.0 25 2.2202 35.8 3.7 -2.9 (-4.0) (-1.2) 15.4 20 2.7753 35.6 4.7 - 1.6 17.3

15 3.7004 35.6 6.2 + 0.3 19.7 12 4.6255 35.4 7.5 1.9 21.6

10 5.5506 35.3 8.3 3.4 22.9

9.5 5.8427 35.3 8.5 3.8 23.3

9.0 6.1674 35.2 8.8 4.3 23.7

8.5 6.5301 35.1 9.1 4.8 24.2

8.0 6.9383 35.1 9.5 5.3 24.7

7.5 7.4008 35.1 9.9 6.0 25.1

7.0 7.9295 35.0 10.2 25.6

6.5 8.5394 34.9 10.6 26.1 6.0 9.2510 34.8 11.2 26.6

5.5 10.0920 34.7 11.8 27.2

5.0 11.1012 34.6 12.5 27.8

4.5 12.3346 34.5 13.3 28.5

4.0 13.8765 34.5 14.1 29.1

3.5 15.8589 34.6 14.9 29.8

3.25 17.0788 34.7 15.3 30.2

3.0 18.5020 34.8 15.7 30.7

2.5 22.2024 35.1 16.1 31.6

2.0 27.7530 35.1 17.4

1.5 37.0040 35.3 18.3

1.0 55.506 35.8 19.2

*Estimated.

45
Table V. Heat capacity: silver and lithium compounds

<t>c. cal/deg mole, at 25 °C

n m AgF AgN03 LiOH LiCl LiBr Lil LiN03

00 0.00 - 20.3 - 15.5 - 19.1 - 16.2 - 17.5 - 17.6 - 4.3 100,000 .000555 - 15.4 - 18.9 - 16.1 - 17.4 - 17.5 - 4.2 50,000 .00111 - 15.3 - 18.8 - 16.0 - 17.3 - 17.4 - 4.1 20,000 .00278 - 15.2 - 18.7 - 15.9 - 17.2 - 17.3 - 4.0 10,000 .00555 - 15.0 - 18.6 - 15.8 - 17.1 - 17.2 - 3.8

7,000 .00793 - 14.9 - 18.5 - 15.7 - 17.0 - 17.1 - 3.7 5,000 .OHIO - 14.8 - 18.3 - 15.6 - 16.9 - 17.0 - 3.6 4,000 .01388 - 14.7 - 18.2 - 15.5 - 16.8 - 16.9 - 3.5 3,000 .01850 - 14.5 - 18.1 - 15.4 - 16.7 - 16.8 - 3.4 2,000 .02775 - 14.2 - 17.9 - 15.2 - 16.5 - 16.5 - 3.2

1,500 .03700 - 13.9 - 17.7 - 15.0 - 16.3 - 16.3 - 3.0 1,000 .05551 - 13.2 - 17.3 - 14.8 - 16.1 - 16.0 - 2.8 900 .0617 - 13.0 - 17.2 - 14.7 - 16.0 - 15.9 - 2.7 800 .0694 - 12.8 - 17.0 - 14.6 - 15.9 - 15.7 - 2.6 700 .0793 - 12.5 - 16.8 - 14.5 - 15.8 - 15.6 - 2.5

600 .0925 - 12.1 - 16.6 - 14.3 - 15.7 - 15.4 - 2.4 500 .1110 - 11.6 - 16.2 - 14.2 - 15.6 - 15.2 - 2.2 400 .1388 - 10.8 - 15.8 - 13.9 - 15.4 - 14.9 - 1.9 300 .1850 - 9.7 - 15.1 - 13.6 - 15.0 - 14.4 - 1.5 200 .2775 - 7.8 - 13.9 - 13.0 - 14.5 - 13.6 - 0.8

150 .3700 - 6.1 - 12.8 - 12.6 - 14.0 - 13.0 - 0.1 100 .5551 - 3.3 - 11.0 - 11.7 - 13.2 - 11.8 + 1.1 75 .7401 - 1.0 - 9.5 - 11.1 - 12.5 - 10.8 2.1 50 1.1101 + 2.9 - 6.9 - 10.0 - 11.5 - 9.3 3.8 40 1.3877 5.5 - 5.3 - 9.4 - 10.8 - 8.4 4.9

30 1.8502 - 2.2 9.2 - 2.9 - 8.5 - 9.7 - 7.2 6.5 25 2.2202 - 2.1 11.8 - 1.2 - 7.8 - 9.0 - 6.4 7.7 20 2.7753 - 1.8 + 1.0 - 6.9 - 8.0 - 5.3 15 3.7004 - 1.5 4.6 - 5.6 - 6.8 *(- 3 . 9 ) 12 4.6255 - 1.4 7.5 - 4.5 - 5.5 (- 2 . 6 )

10 5.5506 - 1.2 - 3.3 - 4.4 (- 1 . 5 ) 9.5 5.8427 - 1.2 - 2.9 - 4.0 (- 1 . 2 ) 9.0 6.1674 - 1.2 - 2.6 - 3.6 (- 0. 9 ) 8.5 6.5301 - 1.2 - 2.2 - 3.2 (- 0 . 5 ) 8.0 6.9383 - 1.1 - 1.8 - 2.8 (— 0. 1 )

7.5 7.4008 - 1.1 - 1.2 - 2.2 (+ 0 . 5 ) 7.0 7.9295 - 1.1 -0 6 - 1.6 ( 1 . 1 ) 6.5 8.5394 - 1.1 + 0.1 - 0.8 ( 1 . 8 ) 6.0 9.2510 - 1.2 0.9 - 0.1 ( 2 . 6 ) 5.5 10.0920 - 1.3 1.7 + 0.8 ( 3 . 4)

5.0 11.1012 - 1.5 2.5 1.7 ( 4 . 4 ) 4.5 12.3346 - 1.6 3.5 2.8 ( 5 . 2 ) 4.0 13.8765 - 1.8 4.5 4.0 ( 6 . 2 ) 3.5 15.8589 5.8 5.3 ( 7 . 4) 3.25 17.0788 6.4 6.1

3.0 18.5020 6.9 6.8

* Estimated .

46
Table VI . Heat capacity: sodium compounds

0c, cal/deg mole, at 25 °C

n m NaOH NaCl NaC103 NaC104 NaBr NaBr03 Nal NaN02 NaN03 NaCH02 Na- C2H3O2

Na- C3H5O2

00 0.00 - 24.4 - 21.5 - 8.6 - 7.1 - 22.8 - 15.4 - 22.9 - 12.2 - 9.6 - 9.9 + 9.6 + 37.8 100,000 .000555 - 24.3 - 21.4 - 8.5 - 7.0 - 22.7 - 15.3 - 22.8 - 12.1 - 9.5 - 9.8 9.7 37.9 50,000 .00111 - 24.2 - 21.3 - 8.4 - 6.9 - 22.6 - 15.2 - 22.7 - 12.0 - 9.4 - 9.7 9.8 38.0 20,000 .00278 - 24.1 - 21.2 - 8.3 - 6.8 - 22.5 - 15.1 - 22.6 - 11.9 - 9.3 - 9.6 9.9 38.1 10,000 .00555 - 23.9 - 21.1 - 8.2 - 6.6 - 22.4 - 15.0 - 22.5 - 11.8 - 9.1 - 9.5 10.0 38.3

7,000 .00793 - 23.8 - 21.0 - 8.1 - 6.5 - 22.3 - 14.8 - 22.4 - 11.7 - 9.0 - 9.3 10.1 38.4

5,000 .OHIO - 23.7 - 20.9 - 7.9 - 6.3 - 22.2 - 14.7 - 22.3 - 11.5 - 8.9 - 9.2 10.3 38.5 4,000 .01388 - 23.6 - 20.8 - 7.8 - 6.2 - 22.1 - 14.6 - 22.2 - 11.4 - 8.8 - 9.1 10.4 38.6 3,000 .01850 - 23.4 - 20.7 - 7.7 - 5.9 - 22.0 - 14.4 - 22.1 - 11.3 - 8.6 - 8.9 10.5 38.7 2,000 .02775 - 23.1 - 20.4 - 7.4 - 5.5 - 21.8 - 14.1 - 21.9 - 11.0 - 8.3 - 8.6 10.8 39.0

1,500 .03700 - 22.8 - 20.2 - 7.1 - 5.0 - 21.6 - 13.7 - 21.7 - 10.7 - 8.0 - 8.3 11.1 39.2

1,000 .05551 - 22.2 - 19.8 - 6.5 - 4.1 - 21.2 - 13.1 - 2 l .2 - 10.2 - 7.4 - 7.7 11.7 39.7 900 .0617 - 22.0 - 19.6 - 6.3 - 3.9 - 21.0 - 12.9 - 21.1 - 10.0 - 7.2 - 7.6 11.8 39.8 800 .0694 - 21.8 - 19.5 - 6.1 - 3.5 - 20.9 - 12.6 - 20.8 - 9.8 - 7.0 - 7.3 12.0 39.9 700 .0793 - 21.5 - 19.3 - 5.7 - 3.0 - 20.7 - 12.3 - 20.6 - 9.5 - 6.7 - 7.0 12.3 40.2

600 .0925 - 21.2 - 19.0 - 5.4 - 2.4 - 20.4 - 11.8 - 20.3 - 9.2 - 6.4 - 6.7 12.6 40.4 500 .1110 - 20.7 - 18.6 - 4.9 - 1.5 - 20.0 - 11.3 - 19.9 - 8.7 - 5.9 - 6.2 13.1 40.8 400 .1388 - 20.0 - 18.2 - 4.1 - 0.1 - 19.6 - 10.4 - 19.2 - 7.9 - 5.2 - 5.5 13.8 41.2 300 .1850 - 18.9 - 17.5 - 2.8 + 1.9 - 18.8 - 9.2 - 18.3 - 6.9 - 4.1 - 4.4 14.6 42.0 200 .2775 - 17.1 - 16.3 - 0.7 5.5 - 17.5 - 7.1 - 16.7 - 5.1 - 2.1 - 2.5 16.4 43/2

150 .3700 - 15.5 - 15.2 + 1.1 8.4 - 16.5 - 5.2 - 15.3 - 3.6 - 0.5 - 1.0 17.9 44.2 100 .5551 - 12.9 - 13.4 4.2 12.7 - 14.4 - 2.1 - 12.9 - 0.9 + 2.2 + 1.6 20.5 45.8

75 .7401 - 10.7 - 11.7 6.6 15.3 - 12.7 + 0.5 - 11.0 + 1.4 4.5 3.6 22.7 46.9 50 1.1101 - 7.1 - 8.8 10.7 18.4 - 9.7 4.9 - 7.6 5.1 8.3 6.8 26.4 48.6 40 1.3877 - 4.8 - 7.0 13.1 20.0 - 7.7 7.4 - 5.4 7.3 10.7 8.7 28.5 49.6

30 1.8502 - 1.7 - 4.6 16.4 22.3 - 4.9 10.8 - 2.4 10.4 14.2 11.6 31.1 50.8 25 2.2202 + 0.4 - 2.4 18.4 23.8 - 3.0 13.1 - 0.4 12.6 16.4 13.6 32.7 51.7 20 2.7753 3.2 0.0 20.7 25.9 - 0.4 + 2.1 15.3 15.8 34.6

15 3.7004 6.8 + 3.3 23.4 28.4 + 2.9 5.6 19.1 18.6 36.9

12 4.6255 9.8 6.3 25.3 30.1 5.8 38.4

10 5.5506 12.2 9.0 26.5 31.2 8.2 39.5

9.5 5.8427 12.8 9.7 26.9 31.4 9.0 39.9

9.0 6.1674 13.5 10.5 27.2 31.7 9.8 40.2

8.5 6.5301 14.3 27.5 32.0 10.7 40.6

8.0 6.9383 15.1 27.8 32.3 11.6 40.9

7.5 7.4008 15.8 28.2 32.6 12.7 41.4

7.0 7.9295 16.6 28.6 32.9 13.8

6.5 8.5394 17.5 29.0 33.3 15.0

6.0 9.2510 18.4 29.4 33.6 16.3

5.5 10.0920 19.1 34.0

5.0 11.1012 19.8 34.4

4.5 12.3346 20.6 34.8

4.0 13.8765 21.3 35.2

3.5 15.8589 22.0 35.5

3.25 17.0788 22.2 35.6

3.0 18.5020 22.3

2.5 22.2024 22.2

2.0 27.7530 21.2

47
Table VII. Heat capacity: potassium compounds

4>c. eal/deg mole, at 25 °C

Tl m KOH KC1 KBr KI kio3 kno3 kc2 h3 o2 KCNS KMn04

00 0.00 - 30.3 - 27.4 - 28.7 - 28.8 - 24.4 - 15.5 + 3.7 - 4.4 - 14.4 100,000 .000555 - 30.2 - 27.3 - 28.6 - 28.7 - 24.2 - 15.3 3.8 - 4.2 - 14.3 50,000 .00111 - 30.1 - 27.2 - 28.5 - 28.6 - 24.1 - 15.3 3.9 - 4.2 - 14.2 20,000 .00278 - 30.0 - 27.1 - 28.4 - 28.5 - 24.0 - 15.1 4.0 - 4.1 - 14.1 10,000 .00555 - 29.9 - 27.0 - 28.3 - 28.4 - 23.6 - 15.0 4.1 - 4.0 - 13.9

7,000 .00793 - 29.8 - 26.9 - 28.2 - 28.3 - 23.5 - 14.9 4.2 - 3.9 - 13.8 5,000 .OHIO - 29.7 - 26.8 - 28.1 - 28.2 - 23.3 - 14.8 4.3 - 3.8 - 13.6 4,000 .01388 - 29.6 - 26.7 - 28.0 - 28.1 - 23.1 - 14.7 4.4 - 3.7 - 13.5 3,000 .01850 - 29.5 - 26.6 - 27.9 - 27.9 - 22.7 - 14.5 4.5 - 3.6 - 13.3 2,000 .02775 - 29.2 - 26.4 - 27.6 - 27.7 - 21.7 - 14.2 4.7 - 3.3 - 12.9

1,500 .03700 - 29.0 - 26.2 - 27.4 - 27.5 - 21.3 - 13.8 4.9 - 3.1 - 12.5 1,000 .05551 - 28.7 - 25.9 - 27.0 - 27.0 - 19.8 - 13.3 5.3 - 2.8 - 11.6 900 .0617 - 28.6 - 25.7 - 26.9 - 26.9 - 19.6 - 13.1 5.4 - 2.7 - 11.4 800 .0694 - 28.4 - 25.6 - 26.7 - 26.7 - 18.7 - 12.8 5.5 - 2.6 - 11.0 700 .0793 - 28.2 - 25.4 - 26.6 - 26.5 - 17.9 - 12.5 5.7 - 2.4 - 10.5

600 .0925 - 28.0 - 25.3 - 26.4 - 26.3 - 16.8 - 12.2 5.9 - 2.2 - 9.9 500 .1110 - 27.6 - 25.0 - 26.1 - 26.0 - 15.2 - 11.7 6.2 - 1.9 - 9.2 400 .1388 - 27.2 - 24.7 - 25.7 - 25.5 - 12.9 - 11.0 6.7 - 1.5 - 8.0 300 .1850 - 26.5 - 24.1 - 25.1 - 24.8 - 9.3 - 9.9 7.4 - 1.0 - 6.2 200 .2775 - 25.3 - 23.3 - 24.0 - 23.5 - 3.6 - 8.1 8.6 0.0 - 2.7

150 .3700 - 24.3 - 22.6 - 23.1 - 22.3 + 1.4 - 6.4 9.8 + 0.8 + 0.1 100 .5551 - 22.6 - 21.2 - 21.6 - 20.4 - 3.8 11.8 2.0 4.7 75 .7401 - 21.1 — 20.0 — 20.4 — 18.8 - 1.6 13.6 3.2 50 1.1101 — 18.6 - 17.8 - 18.3 - 16.3 + 2.1 16.5 4.9 40 1.3877 - 16.9 — 16.4 — 17.0 — 14.8 4.4 18.2 6.0

30 1.8502 - 14.4 - 14.3 - 14.9 - 12.7 7.9 20.4 7.6 25 2.2202 - 12.5 - 12.8 — 13.4 - 11.2 10.3 21.9 8.7 20 2.7753 - 10.8 - 11.4 — 9.3 13.5 23.5 10.2 15 3.7004 - 8.1 - 8.7 17.7 25.3

12 4.6255 - 6.0 - 6.5 26.5

10 5.5506 - 4.2 - 4.6 27.5

9.5 5.8427 - 4.2 27.8

9.0 6.1674 28.1

8.5 6.5301 28.5

8.0 6.9383 28.8

7.5 7.4008 29 2

7.0 7.9295 29.6

6.5 8.5394 n

6.0 9.2510 30.4

5.5 10.0920 o

5.0 11.1012 31.5

48
Table VIII. Heat capacity: rubidium compounds

Or, cal/deg mole, at 25 °C

n m RbOH* RbCl* RbBr* Rbl* RbN03 *

00 0.00 (-32.2) (- 29.3) (- 30.6) (-30.7) (- 17.4) 100,000 .000555 (-32.1) (- 29.2) (- 30.5) (-30.6) (-17.3)

50,000 .00111 (-32.0) (-29.1) (- 30.4) (- 30.5) (-17.2)

20,000 .00278 (-31.9) (-29.0) (- 30.3) (- 30.4) (-17.1)

10,000 .00555 (-31.8) (- 28.9) (- 30.2) (-30.3) (-17.0)

7,000 .00793 (-31.7) (- 28.8) (-30.1) (- 30.2) (- 16.9) 5,000 .OHIO (-31.6) (- 28.7) (- 30.0) (-30.1) (-16.8)

4,000 .01388 (-31.5) (- 28.6) (- 29.9) (- 30.0) (-16.7)

3,000 .01850 (-31.4) (- 28.5) (-29.8) (- 29.9) (- 16.5) 2,000 .02775 (-31.1) (-28.3) (-29.6) (-29.7) (- 16.2)

1,500 .03700 (- 30.9) (- 28.2) (-29.4) (-29.5) (- 15.9) 1,000 .05551 (- 30.5) (- 28.0) (- 29.2) (-29.1) (- 15.3) 900 .0617 (- 30.4) (- 27.9) (-29.1) (- 29.0) (-15.1)

800 .0694 (-30.2) (- 27.8) (- 29.0) (- 28.9) (- 14.9) 700 .0793 (- 30.0) (- 27.6) (- 28.8) (- 28.7) (-14.6)

600 .0925 (- 29.8) (- 27.5) (-28.7) (- 28.5) (- 14.3) 500 .1110 (-29.5) (- 27.3) (- 28.5) (-28.2) (- 13.8) 400 .1388 (- 29.1) (- 27.0) (-28.2) (- 27.8) (- 13.0) 300 .1850 (- 28.4) (- 26.6) (- 27.7) (- 27.3) (-12.0)

200 .2775 (- 27.3) (- 25.8) (-26.9) (- 26.3) (-10.1)

150 .3700 (- 26.2) (-25.1) (- 26.2) (-25.4) (-8.6)

100 .5551 (- 24.4) (- 24.0) (- 25.0) (- 23.9) (-5.8) 75 .7401 (-22.9) (- 23.1) (- 24.0) (- 22.6) (-3.6) 50 1.1101 (- 20.2) (-21.5) (-20.3) (+0.2)

*Estimated.

Table IX. Heat capacity: cesium compounds

Oc, cal/deg mole, at 25 °C

n m CsOH* CsCl* CsBr* Csl CsNOa*

00 0.00 -33.6 -30.7 -32.0 -32.1 -18.8

100,000 .000555 (-33.5) (-30.6) (-31.9) -32.0 (-18.7)

50,000 .00111 (- 33.5) (- 30.5) (-31.8) -31.9 (- 18.6) 20,000 .00278 (- 33.4) (-30.4) (-31.7) -31.8 (- 18.5) 10,000 .00555 (- 33.3) (-30.3) (-31.6) -31.7 (- 18.4)

7,000 .00793 (- 33.2) (-30.3) (-31.5) -31.6 (- 18.3) 5,000 .OHIO (-33.1) (- 30.2) (-31.4) -31.5 (- 18.2) 4,000 .01388 (-33.0) (-30.1) (-31.3) -31.4 (-18.1)

3,000 .01850 (-32.9) (-30.0) (-31.2) -31.3 (- 17.9) 2,000 .02775 (-32.7) (-29.8) (-31.0) -31.1 (-17.6)

1,500 .03700 (-32.4) (-29.6) (- 30.8) -30.9 (-17.3)

1,000 .05551 (-32.1) (- 29.3) (-30.5) -30.6 (- 16.7) 900 .0617 (-31.9) (- 29.2) (- 30.4) -30.5 (- 16.5) 800 .0694 (-31.8) (-29.1) (- 30.3) -30.4 (-16.3) 700 .0793 (-31.6) (- 29.0) (-30.2) -30.2 (- 16.0) 600 .0925 (-31.4) (-28.8) (-30.0) -30.0 (-15.7)

500 .1110 (-31.1) (- 28.6) (- 29.8) -29.7 (- 15.2) 400 .1388 (-30.7) (- 28.3) (-29.5) -29.3 (- 14.4) 300 .1850 (-30.1) (- 27.9) (-29.1) -28.7 (- 13.4) 200 .2775 (-29.1) (-27.2) (-28.3) -27.7 (-11.5) 150 .3700 (-28.0) (-26.6) (-27.6) -26.9 (-9.7)

100 .5551 (- 26.4) (-25.5) (-26.5) -25.5 (-7.2)

75 .7401 (-25.0) (- 24.6) (- 25.5) -24.5 (-5.0) 50 1.1101 (- 22.3) (-23.1) (-23.8) -22.6 (-1.2) 40 1.3877 (-20.6) (-22.1) (-22.7) -21.4 (+1.2) 30 1.8502 (-17.5) — 19.7 25 2.2202 (- 15.7) - 18.3

"“Estimated. 49
Table X. Thermal properties of aqueous NaCl at 25 °C

n m d&Jdm112 U

00 0.00 472

callmole

0

cal/mole

0

100,000 .000555 436 11 16 50,000 .00111 423 14 21 20,000 .00278 395 22 32

10,000 .00555 365 31 45

7,000 .00793 344 37 52

5,000 .OHIO 322 42 59

4,000 .01388 304 46 64

3,000 .01850 282 51 70

2,000 .02775 245 59 79

1,000 .05551 167 73 93

900 .0617 155 75 94

800 .0694 139 78 96

700 .0793 120 80 97

600 .0925 99 83 98

500 .1110 71 85 97

400 .1388 + 35 87 94

300 .1850 -14 88 85

200 .2775 -87 83 + 60

100 .5551 -220 49 -33

75 .7401 -275 + 20 -98

50 1.1101 -344 -41 -222

40 1.3877 -373 -85 -304

30 1.8502 -394 -156 -424

25 2.2202 -394 -207 -501

20 2.7753 -376 -274 -587

15 3.7004 -321 -367 -676

12 4.6255 -242 -430 -690

10 5.5506 -135 -469 -628

9.5 5.8427 -93 -476 -588

Table XI. Heat of dilution: acids

<J>l, cal/mole, at 25 °C

n m HF HC1 HC104 HBr HI HN03 ch2 o2 c2 h4o2

00 0.00 0 0 0 0 0 0 0 0

500,000 .000111 300 5 5 5 5 5 9 40

100,000 .000555 900 10 10 9 9 11 13 50

50,000 .00111 1,300 16 14 13 12 15 20 53

20,000 .00278 1,800 25 22 22 20 23 23 55

10,000 .00555 2,130 34 30 31 29 31 25 58

7,000 .00793 2,250 40 35 37 34 36 26 59

5,000 .OHIO 2,360 47 40 44 41 42 26 61 4,000 .01388 2,450 54 43 49 46 46 27 62

3,000 .01850 2,550 60 47 56 52 51 28 62

2,000 .02775 2,700 74 54 68 63 59 28 63

1,500 .03700 2,812 85 58 77 71 65 29 64

1,110 .05000 2,927 97 62 89 81 73 29 65

1,000 .05551 2,969 102 62 92 84 76 29 65

900 .0617 2,989 107 63 97 88 78 30 66

800 .0694 3,015 113 64 102 92 81 31 67

700 .0793 3,037 120 65 108 96 84 32 68

600 .0925 3,057 129 65 115 102 88 32 68

555.1 .1000 3,060 133 65 119 105 89 32 69

500 .1110 3,077 140 65 124 108 92 32 70 400 .1388 3,097 156 64 135 116 97 33 72

50
Table XI. Heat of dilution: acids—Continued

<I>i, cal/mole, at 25 °C

n m HF HC1 HC104 HBr HI hno3 ch2 o2 c2h4 o2

300 .1850 3,126 176 61 150 125 103 34 76

277.5 .2000 3,129 182 59 155 128 105 35 79 200 .2775 3,142 212 50 176 140 117 36 82

150 .3700 3,148 242 36 197 154 118 39 88

111.0 .5000 3,156 280 18 225 170 119 42 97

100 .5551 3,160 295 + 12 235 176 120 44 101 75 .7401 3,167 343 -14 270 194 121 49 113

55.51 1.0000 3,179 405 -48 314 223 121 54 130 50 1.1101 3,184 431 -61 331 234 121 56 147 40 1.3877 3,192 493 -91 379 260 121 60 155

37.00 1.5000 3,194 518 -103 398 269 121 62 162 30 1.8502 3,200 595 -138 455 301 124 65 183

27.75 2.0000 3,203 627 -149 477 315 126 66 192 25 2.2202 3,208 674 -162 510 336 130 67 204

22.20 2.5000 3,211 732 -173 550 365 139 68 218

20 2.7753 3,214 792 -182 590 396 149 69 233

18.50 3.0000 3,216 838 -187 624 427 159 69 245

15.86 3.5000 3,221 946 -196 709 503 189 69 268

15 3.7004 3,227 988 -195 743 536 203 69 277

13.88 4.0000 3,234 1,052 -188 796 588 229 69 291

12.33 4.5000 3,246 1,171 -175 887 676 265 69 313

12 4.6255 3,249 1,190 -170 911 700 277 69 318

11.10 5.0000 3,256 1,271 -150 983 764 313 69 333

10 5.5506 3,265 1,396 -117 1,097 855 368 68 353

9.5 5.8427 3,269 1,462 -97 1,156 920 400 68 363

9.251 6.0000 3,272 1,498 -84 1,196 950 418 67 368

9.0 6.1674 3,274 1,535 -72 1,230 980 437 67 373

8.5 6.5301 3,278 1,618 -40 1,313 1,050 480 66 383

8.0 6.9383 3,282 1,710 ~b 4 1,401 1,115 530 65 392

7.929 7.0000 3,283 1,725 11 1,416 1,130 538 65 394

7.5 7.4008 3,286 1,820 61 1,497 1,210 595 63 402

7.0 7.9295 3,290 1,942 135 1,608 1,325 661 61 411

6.938 8.0000 3,291 1,960 146 1,622 1,340 667 61 412

6.5 8.5394 3,296 2,090 229 1,738 1,450 745 58 420

6.167 9.0000 3,302 2,202 306 1,845 1,570 805 55 426

6.0 9.2510 3,305 2,265 348 1,903 1,630 840 53 429

5.551 10.0000 3,316 2,447 481 2,078 1,820 940 49 436

5.5 10.0920 3.317 2,472 499 2,102 1,850 950 49 437

5.0 11.1012 3,335 2,721 730 2,344 2,100 1,098 43 445

4.5 12.3346 3,362 3,025 1,144 2,655 2,460 1,270 37 453

4.0 13.8765 3,400 3,404 1,574 3,089 2,960 1,495 29 462

3.700 15.0000 3,428 3,680 1,893 3,415 3,350 1,645 26 469

3.5 15.8589 3,450 3,882 2,150 3,668 3,660 1,770 21 473

3.25 17.0788 3,483 4,160 2,460 4,005 4,110 1,920 17 481

3.0 18.5020 3,520 4,460 2,880 4,370 4,630 2,101 13 488

2.775 20.0000 3,557 4,750 3,300 4,760 5,190 2,270 9 496

2.5 22.2024 3,607 5,180 4,000 5,300 6,000 2,520 4 506

2.0 27.7530 3,712 6,260 5,500 6,650 3,060 -5 528

1.5 37.0040 8,240 8,530 3,770 - 13 532

1.0 55.506 10'900 11,670 4,715 + 11 518

0.5 111.012 77 495

0.25 222.02 129

51
Table XII A. Heat of dilution: ammonium compounds

4*1, cal/mole, at 25 °C

n m NH4 OH nh3 NH4CI NH4 Br* NH4I* NH4NO3 nh4c2h3o2

00 0.00 0 0 0 0 0 0 0

500,000 .000111 -584 -584 5 (5) (5) 5 100,000 .000555 -722 -722 10 (10) (10) 10 82

50,000 .00111 -761 -761 14 (14) (13) 14 86

20,000 .00278 -800 -800 22 (22) (21) 22 95

10,000 .00555 -815 -815 29 (29) (28) 28 105

7,000 .00793 -824 -824 34 (33) (32) 32 112 5,000 .OHIO -829 -829 40 (39) (38) 36 119 4,000 .01388 -833 -833 44 (43) (42) 39 125 3,000 .01850 -838 -838 48 (46) (44) 43 134

2,000 .02775 -841 -841 57 (55) (53) 48 147

1,500 .03700 -844 -844 63 (61) (59) 50 159

1,110 .05000 -846 -846 70 (65) (63) 52 174

1,000 .05551 -846 -846 73 (70) (68) 53 180 900 .0617 -846 -846 76 (73) (71) 53 185 800 .0694 -846 -846 79 (74) (72) 53 193

700 .0793 -847 -847 82 (76) (73) 52 201 600 .0925 -847 -847 87 (80) (74) 51 212

555.1 .1000 -847 -847 88 (82) (76) 49 217 500 .1110 -848 -848 92 (86) (80) 47 225

400 .1388 -849 -849 98 (90) (82) 41 243

300 .1850 -848 — 848 105 (95) (85) 27 272

277.5 .2000 -848 -848 107 (96) (84) + 23 279

200 .2775 -846 -845 117 (100) (80) -2 315

150 .3700 -845 -844 124 (105) (78) -36 355

111.0 .5000 -843 -842 131 (106) (77) -88 404

100 .5551 -843 -842 133 (106) (76) -110 423

75 .7401 -840 — 838 136 - 182 480

55.51 1.0000 -835 -833 136 -270 551 50 1.1101 -834 -831 136 -308 579

40 1.3877 -830 -827 134 -396 644

37.00 1.5000 -824 -821 133 -442 699

30 1.8502 — 818 — 815 128 -535 740

27.75 2.0000 -816 -813 125 -575 769

25 2.2202 -814 -811 120 -636 810

22 20 2.5000 — 808 — 805 114 -704 850

20 2.7753 -803 — 800 108 -770 895

18.50 3.0000 -798 — 795 104 -810 930

15 86 3.5000 -790 — 786 93 -910 1,000 15 3.7004 -787 — 783 89 -950 1,040 13.88 4.0000 — 782 — 777 82 -1,000 1,069

12.33 4.5000 -774 — 768 72 -1,085 1,130 12 4.6255 — 772 — 765 69 -1,106 1,145 11.10 5.0000 -766 — 759 62 -1,165 1,190

10 5.5506 — 756 — 749 53 -1,240 1,250

9.5 5.8427 -754 — 744 48 - 1,285 1,290

9.251 6.0000 — 752 — 741 45 -1,308 1,310

9.0 6.1674 — 749 — 737 42 - 1,330 1,330

8.5 6.5301 -744 — 730 36 -1,375 1,370

8.0 6.9383 -737 — 721 30 -1,430 1,425 7.929 7.0000 -736 -720 29 - 1,436 1,434

"Footnote at end of table.

52
Table XII A. Heat of dilution: ammonium compounds — Continued

<t>i, cal/mole, at 25 °C

n m NH4OH nh3 NH4 C1 NH4 Br* NHJ* nh4 no3 nh4 c2h3o2

7.5 7.4008 -730 — 711 - 1,485 1,478

7.0 7.9295 -721 -698 - 1,545 1,536 6.938 8.0000 -720 -696 -1,550 1,542

6.5 8.5394 -711 — 684 -1,605 1,600 6 167 9.0000 — 703 -672 - 1,650 1,646

6.0 9.2510 -698 -667 -1,675 1,670

5.551 10.0000 -686 -648 - 1,738 1,732

5 5 10.0920 — 684 — 646 - 1,745 1,740

5 0 11.1012 — 667 — 620 - 1,820 1,810

4.5 12.3346 -646 -588 -1,900 1,884

4.0 13.8765 -620 -548 -1,988 1,950 3.700 15.0000 -602 -520 -2,048 1,986

3.5 15.8589 -588 — 498 - 2,090 2,008

3.25 17.0788 -570 -471 -2,150 2,034

3.0 18.5020 -548 -438 - 2,255 2,060

2.775 20.0000 -530 — 405 - 2,320 2,082

2.5 22.2024 — 498 -358 2,110

2.0 27.7530 -438 -235 2,168

1.5 37.0040 — 358 — 39

1.0 55.506 -235 + 314

* Estimated.

Table XII B. Heat of dilution: alkyl ammonium compounds

<t>i, cal/mole, at 25 °C

n m (CH3)NH3 C1 (CH3) 2NH2C1 (CH3)3 NHC1 N(CH3)4 C1 NH2 CH3 NH(CH3) 2 N(CH3)3

00 0.00 0 0 0 0

500,000 .000111 5 5 5 5 100,000 .000555 10 10 10 10 50,000 .00111 14 14 13 13 20,000 .00278 23 23 21 20

10,000 .00555 30 30 26 23

7,000 .00793 36 34 30 25

5,000 .OHIO 41 39 34 27

4,000 .01388 45 43 36 27

3,000 .01850 50 48 39 27

2,000 .02775 61 56 44 24

1,500 .03700 68 61 44 19 1,110 .05000 76 68 45 14

1,000 .05551 79 70 45 10 0 0 0 900 .0617 82 72 45 7 20 800 .0694 85 75 45 + 1 50

700 .0793 89 77 44 -5 80 100 100 600 .0925 93 81 43 -13 110

555.1 .1000 96 82 42 -18 120 500 .1110 99 84 41 -24 130 400 .1388 105 88 38 -41 160 200 200

300 .1850 113 92 31 -67 210

277.5 .2000 115 94 29 -75

200 .2775 123 98 18 -110

150 .3700 131 102 + 2 -158

111.0 .5000 139 106 -13 -211

100 .5551 143 107 -24 -232

75 7401 152 112 — 46

55 51 1 0000 164 119 — 72 50 1.1101 167 121 -82

53
Table XIII. Heat of dilution: silver and lithium compounds

cal/mole, at 25 °C

n m AgF AgN03 LiOH LiF LiCl LiC104 LiBr Lil* LiN03

00 0.00 0 0 0 0 0 0 0 0

500,000 .000111 4 5 5 5 5 5 (5) 5

100,000 .000555 9 11 11 10 10 10 (10) 10 50,000 .00111 12 16 16 14 14 13 (13) 13 20,000 .00278 17 25 25 23 23 21 (20) 20

10,000 .00555 19 35 35 32 31 29 (28) 28

7,000 .00793 21 42 42 37 37 34 (32) 33

5,000 .OHIO 21 49 49 43 43 40 (38) 38

4,000 .01388 21 55 54 48 48 44 (42) 42

3,000 .01850 20 62 62 54 55 50 (51) 49

2,000 .02775 16 74 76 65 65 60 (55) 58

1,500 .03700 12 84 87 73 73 67 (62) 65

1,110 .05000 5 97 101 82 82 76 (71) 74

1,000 .05551 + 2 102 105 86 85 80 (74) 76 900 .0617 -1 106 110 89 88 83 (77) 80

800 .0694 -6 112 94 92 86 (78) 83

700 .0793 -13 120 99 97 92 (85) 88 600 .0925 -20 127 105 103 97 (89) 93

555.1 .1000 -25 132 108 106 100 (92) 96 500 .1110 -32 139 113 110 105 (97) 100 400 .1388 0 -49 153 124 119 115 (106) 107

300 .1850 1 -79 175 140 133 130 (120) 120

277.5 .2000 1 -88 181 144 137 134 (124) 123 200 .2775 2 -137 211 165 154 155 (145) 139 150 .3700 3 -196 240 186 170 176 (166) 153

111.0 .5000 5 -274 275 213 186 202 (192) 171

100 .5551 6 -307 289 223 192 212 (202) 177

75 .7401 9 -408 329 255 207 243 (232) 194

55.51 1.0000 12 -536 378 296 230 280 (267) 212

50 1.1101 14 -585 396 312 240 295 (280) 218

40 1.3877 18 440 352 263 330 234

37.00 1.5000 20 457 367 272 344 240

30 1.8502 25 508 415 300 386 254

27.75 2.0000 27 528 435 313 403 261 25 2.2202 31 558 465 334 429 271 22.20 2.5000 36 597 504 361 463 281

20 2.7753 41 635 542 390 496 *(293) 18.50 3.0000 45 667 575 414 524 (302) 15.86 3.5000 54 738 645 469 588 (329)

15 3.7004 58 766 674 491 614 (342) 13.88 4.0000 64 810 720 523 652 (363)

12.33 4.5000 72 882 799 716 (403)

12 4.6255 76 900 820 733 (415) 11.10 5.0000 87 880 785 (450) 10 5.5506 112 974 864 (500)

9.5 5.8427 128 1,025 905 (530)

9.251 6.0000 138 1,054 930 (550)

9.0 6.1674 144 1,083 953 (570)

8.5 6.5301 172 1,148 1,009 (608)

8.0 6.9383 200 1,225 1,069 (660) 7.929 7.0000 204 1,236 1,079 (670)

^Footnote at end of table.

54
Table XIII. Heat of dilution: silver and lithium compounds — Continued

<I>i, cal/mole, at 25 °C

n m AgF AgN03 LiOH LiF LiCl LiC104 LiBr Lil* LiNOa

7.5 7.0 6.938

6.5 6.167

6.0 5.551

5.5 5.0

4.5

4.0 3.700

3.5 3.25

3.0

7.4008 7.9295 8.0000

8.5394

9.0000

9.2510

10.0000

10.0920

11.1012

12.3346

13.8765 15.0000

15.8589

17.0788 18.5020

238

276

282 329

373

398

474

484

600

748

945

1,313

1,416

1,431

1,542

1,640

1,694

1,858

1,880

2,115

2,411

2,794

3,070

3,282

3,573

3,893

1,140

1,228

1,238

1,332

1,415

1,463

1,611

1,630

1,848

2,147

2,571

2,907

3,171

3,539

(720)

(790)

(800)

(870)

(920)

(970)

(1,070)

(1,080)

(1,230)

* Estimated.

Table XIV A. Heat of dilution: sodium compounds

cal/mole, at 25 °C

n m NaOH NaF* NaCl NaClOa NaC104 NaBr NaBr03

00 0.00 0 0 0 0 0 0 0 500,000 .000111 5 (5) 5 5 5 5 5 100,000 .000555 11 (ID 11 10 10 11 10 50,000 .00111 15 (15) 14 14 14 14 14 20,000 .00278 23 (23) 22 21 21 21 20

10,000 .00555 32 (32) 31 27 27 30 26

7,000 .00793 38 (38) 37 32 31 35 30

5,000 .OHIO 44 (44) 42 36 35 40 33

4,000 .01388 49 (49) 46 39 38 44 36

3,000 .01850 55 (55) 51 42 41 49 38

2,000 .02775 65 (65) 59 45 44 56 40

1,500 .03700 72 (72) 64 47 46 60 39

1,110 .05000 81 (81) 71 47 46 66 37

1,000 .05551 84 (84) 73 47 44 68 36 900 .0617 87 (87) 75 47 44 69 35 800 .0694 90 (90) 78 46 42 71 34

700 .0793 95 (95) 80 45 42 72 32 600 .0925 99 (99) 83 42 38 74 28

555.1 .1000 101 (101) 84 40 36 75 26 500 .1110 104 (104) 85 37 32 75 22 400 .1388 110 (110) 87 29 22 76 + 12

300 .1850 116 (115) 88 11 4 74 *(-6)

277.5 .2000 117 (116) 87 + 7 -2 73 (-13)

200 .2775 121 (119) 83 -22 -37 66 (-46)

150 .3700 118 (115) 74 -58 -80 54 (-88)

111.0 .5000 115 (110) 57 -109 -140 32 (- 145)

100 .5551 112 (107) 49 -130 -167 + 23 (- 170) 75 .7401 99 (92) + 20 -200 -250 -10 (-247)

55.51 1.0000 78 (69) -23 -293 -360 -59 (-350)

50 1.1101 67 (57) -41 -333 -404 -81 (- 388)

40 1.3877 44 -85 -425 -508 -134

‘Footnote at end of table. 55
Table XIV A. Heat of dilution: sodium compounds — Continued

<1>l, cal/mole, 25 °C

n m NaOH NaF* NaCl NaClOa NaC104 NaBr NaBrOs

37.00 1.5000 36 -104 -462 -551 -155

30 1.8502 13 -156 -570 -672 -219

27.75 2.0000 -172 -613 -719 -245

25 2.2202 -4 -207 -675 -787 -282

22.20 2.5000 -14 -242 -747 -866 -326

20 2.7753 -20 -274 -814 -945 -368

18.50 3.0000 -22 -299 -866 -1,004 -400

15.86 3.5000 -16 -349 -973 —

l' 133 -465

15 3.7004 -10 -367 - 1,012 - 1,179 -489

13.88 4.0000 0 -390 - 1,068 - 1,243 -523

12.33 4.5000 + 26 -423 - 1,156 - 1,339 -574

12 4.6255 34 -430 - 1,177 -1,360 -586

11.10 5.0000 61 -449 - 1,234 - l’424 -618

10 5.5506 112 -469 - 1,310 - 1,508 -659

9.5 5.8427 142 -476 - 1,348 - 1,549 -677

9.251 6.0000 161 -479 — 1,369 -1,568 -686

9.0 6.1674 181 -480 - 1,389 - 1,590 -694

8.5 6.5301 229 - 1,430 - 1,632 -711

8.0 6.9383 289 - 1,473 - E676 -725

7.929 7.0000 299 - 1,479 - 1,683 -726

7.5 7.4008 364 - 1,518 - 1,725 -735

7.0 7.9295 457 - 1,566 - 1,777 -741

6.938 8.0000 469 - 1,574 - 1’783 -741

6.5 8.5394 575 - 1,621 - 1,833 -738

6.167 9.0000 672 - 1,658 - 1,872 -730

6.0 9.2510 727 - 1,678 -1,892

5.551 10.0000 903 - 1*945

5.5 10.0920 926 -1,951

5.0 11.1012 1,178 -2,006

4.5 12.3346 1,513 -2,058

4.0 13.8765 1,955 -2,109

3.700 15.0000 2,290 -2*139

3.5 15.8589 2

'543 -2,159

3.25 17.0788 2,903 -2J85

3.0 18.5020 3,307

2.775 20.0000 3,722

2.5 22.2024 4,260

* Estimated.

56
Table XIV B. Heat of dilution: sodium compounds

<j>L, cal/mole, at 25 °C

n m Nal NaI03 NaN02 NaN03 NaC2H3 02 NaCNS

00 0.00 0 0 0 0 0

500,000 .000111 5 5 5 5 5 100,000 .000555 11 10 11 12 11 50,000 .00111 14 12 15 16 14 20,000 .00278 21 17 22 25 22

10,000 .00555 30 21 28 35 29

7,000 .00793 34 22 32 41 33

5,000 .OHIO 39 22 35 48 38

4,000 .01388 43 21 37 54 41 3,000 .01850 48 20 40 62 46

2,000 .02775 54 13 44 75 51

1,500 .03700 58 + 6 44 86 54

1,110 .05000 64 -5 44 91 58

1,000 .05551 66 -11 44 104 58

900 .0617 67 -15 43 109 59 800 .0694 69 -23 41 116 60

700 .0793 70 -33 39 124 59

600 .0925 71 -46 35 132 58

555.1 .1000 72 -54 31 137 57 500 .1110 72 -65 29 143 55 400 .1388 71 + 18 159 50

300 .1850 68 40 -2 180 43

277.5 .2000 66 + 30 -8 187 40

200 .2775 55 -40 -43 215 + 21 150 .3700 39 -100 -86 243 -3

111.0 .5000 12 -170 -147 274 -39

100 .5551 + 1 -190 -173 286 -55

75 .7401 -39 -250 -255 318 -107

55.51 1.0000 -97 -310 -367 358 -179

50 1.1101 -122 -330 -412 372 -208

40 1.3877 -184 -375 -519 407 -277

37.00 1.5000 -209 -390 -560 421 -306

30 1.8502 -283 -420 -678 459 -384

27.75 2.0000 -313 -425 -724 474 -415

25 2.2202 -358 f,. -450 -791 494 -460

22.20 2.5000 -410 -475 -869 522 -513

20 2.7753 -462 -490 -939 556 -564

18.50 3.0000 -501 -510 -994 564 -603

15.86 3.5000 -582 -540 -1,134 620 -686

15 3.7004 -613 -545 -1,144 645 -718

13.88 4.0000 -656 -560 -1,200 675 -763

12.33 4.5000 -719 -585 -1,284 732 -834

12 4.6255 -734 -590 - 1,303 750 -852

11.10 5.0000 -775 -605 -1,359 794 -901

10 5.5506 -828 -630 - 1,431 870 -966

9.5 5.8427 -854 -640 -1,464 914 -997

9.251 6.0000 -866 -645 - 1,483 936 -1,014

9.0 6.1674 -878 -650 -1,501 966 - 1,029

8.5 6.5301 -902 -665 -1,536 1,016 -1,060

8.0 6.9383 -924 -675 -1,573 1,100 -1,092

7.929 7.0000 -927 -680 -1,578 1,108 -1,096

57
Table XIV B. Heat of dilution: sodium compounds — Continued

<!>l, cal/mole. at 25 °C

n m Nal NaI03 NaN02 NaN03 NaC2 H302 NaCNS

7.5 7.4008 -943 -690 - 1,608 1,180 -1,122

7.0 7.9295 -957 -700 -1,644 1,280 -1,149

6.938 8.0000 -959 -710 -1,648 1,290 -1,152

6.5 8.5394 -964 -720 - 1,678 1,394 -1,173

6.167 9.0000 -963 -735 -1,699 1,480 -1,187

6.0 9.2510 -959 -740 - 1,708 1,530 -1,193

5 551 10 0000 -941 -760 1,674 -1,201

5 5 10 0920 -938 -765 1,692 -1,202

5 0 11 1012 -891 -785 1,890 -1,197

4 5 12 3346 -805 -810 2,120 -1,175

4 0 13 8765 2,410 -1,144

3.700 15.0000 2,612 -1,113

3 5 15.8589 2,760

3 25 17 0788 2,980

3.0 18.5020 3,230

Table XV A. Heat of dilution: potassium compounds

<!>£,» cal/mole, at 25 °C

n m KOH KF KC1 KC103 KCIO4 KBr KBrOs*

00 0.00 0 0 0 0 0 0 0 500,000 .000111 5 5 5 5 4 5 (5) 100,000 .000555 11 11 10 10 9 10 (10)

50,000 .00111 16 15 14 13 12 14 (13)

20,000 .00278 23 23 22 20 15 21 (20)

10,000 .00555 32 32 31 24 16 29 (24)

7,000 .00793 38 38 36 27 16 34 (26)

5,000 .OHIO 44 44 41 28 14 38 (26)

4,000 .01388 50 49 45 29 11 42 (25)

3,000 .01850 56 56 50 30 + 5 46 (24)

2,000 .02775 67 67 57 27 -9 53 (21)

1,500 .03700 75 75 62 20 -22 57 (17)

1,110 .05000 86 86 68 17 -40 61 (8) 1,000 .05551 89 89 70 14 -49 63 (4) 900 .0617 92 92 72 11 -58 64 (0) 800 .0694 97 96 74 + 5 -69 65 (-6)

700 .0793 102 101 77 -2 -84 66 (-13)

600 .0925 108 107 79 -12 -103 67 (-24)

555.1 .1000 111 110 80 -14 -113 67 (-30)

500 .1110 115 113 82 -27 67 (-40)

400 .1388 124 121 84 -50 67

300 .1850 134 132 85 -94 64

277.5 .2000 138 135 85 -108 62 200 .2775 151 146 81 -193 53

150 .3700 161 154 72 -310 38

110.0 .5000 172 162 57 -480 13

100 .5551 176 165 50 -546 + 2 75 .7401 186 171 + 23 -37

55.51 1.0000 200 178 -15 -96

50 1.1101 204 181 -32 - 120 40 1.3877 218 187 -73 -179

37.00 1.5000 224 189 -89 -203

30 1.8502 240 195 -139 -273

27.75 2.0000 246 198 -162 -302

25 2.2202 256 203 -190 -343

22.20 2.5000 268 208 -228 -393

*Footnote at end of table. 58
Table XV A. Heat of dilution: potassium compound — Continued

<t>L. cal/mole, at 25 °C

n m KOH KF KC1 KC103 KCIO4 KBr KBrO*

20 2.7753 283 213 -263 -440

18.50 3.0000 299 218 -289 -476

15.86 3.5000 347 233 -344 -555

15 3.7004 370 241 -365 — 584

13.88 4.0000 407 253 -395 -628

12.33 4.5000 476 276 -440 -696

12 4.6255 494 284 -450 -714

11.10 5.0000 548 306 -480 -760

10 5.5506 633 342 — 825

9.5 5.8427 679 364

9.251 6.0000 706 377

9.0 6.1674 732 389

8.5 6.5301 792 420

8.0 6.9383 860 458

7.929 7.0000 870 464

7.5 7.4008 940 504

7.0 7.9295 1,032 559

6.938 8.0000 1,045 568

6.5 8.5394 1,138 629

6.167 9.0000 1,216 686

6.0 9.2510 1,262 719

5.551 10.0000 1,391 817

5.5 10.0920 1,407 830

5.0 11.1012 1,592 970

4.5 12.3346 1,881 1,150

4.0 13.8765 2f251 1,379 3.700 15.0000 2,485 1,543

3.5 15.8589 2,646 1,665 3.25 17.0788 2,860

3.0 18.5020 3,086

* Estimated.

Table XV B. Heat of dilution: potassium compounds

4>l, cal/mole, at 25 °C

n m KI KI03* KNOs kc2 h3o2 KCNS KMn04

00 0.00 0 0 0 0 0 0

500,000 .000111 5 (5) 5 5 5 4 100,000 .000555 10 (10) 10 12 11 7 50,000 .00111 14 (12) 14 16 14 9

20,000 .00278 21 (16) 19 25 22 13 10,000 .00555 29 (20) 23 35 29 13

7,000 .00793 33 (19) 24 42 33 12 5,000 .OHIO 37 (18) 25 49 38 9

4,000 .01388 41 (16) 25 55 40 6

3,000 .01850 45 (13) 24 63 45 + 1 2,000 .02775 51 (+6) 19 76 49 -13

1,500 .03700 53 (-5) 14 87 52 -24

1,110 .05000 57 (-21) 4 93 55 -42

1,000 .05551 57 (-29) + 1 107 56 -50

900 .0617 58 (-38) -4 112 56 -58

800 .0694 59 (-47) -11 119 56 -67

700 .0793 59 (-62) -20 127 56 -81

600 .0925 58 (-82) -31 136 55 -96

555.1 .1000 57 (-95) -38 141 54 -105

500 .1110 57 (-122) -48 148 52 -117

400 .1388 53 -73 165 47 -149

Footnote at end of table. 59
TABLE XV B. Heat of dilution: potassium compounds — Continued

*Estimated.

60
Table XVI. Heat of dilution: rubidium and cesium compounds

<t>L< cal/mole, at 25 °C

n m RbF RbCl* RbBr* Rbl* RbNOs* CsF* CsCl CsBr* Csl* CsN03

00 0.00 0 0 0 0 0 0 0 0 0 0

500,000 .000111 5 (5) (5) (5) (5) (5) 5 (5) (5) 4

100,000 .000555 10 (10) (10) (10) (10) (10) 10 (10) (10) 9

50,000 .00111 13 (13) (13) (13) (13) (13) 13 (13) (13) 12 20,000 .00278 21 (21) (20) (20) (17) (20) 21 (20) (20) 15 10,000 .00555 29 (28) (26) (26) (20) (27) 28 (26) (26) 17

7,000 .00793 34 (34) (32) (31) (22) (31) 32 (30) (29) 17 5,000 .OHIO 39 (39) (36) (35) (22) (35) 36 (33) (32) 16 4,000 .01388 43 (42) (39) (38) (24) (39) 39 (36) (35) 14 3,000 .01850 48 (47) (43) (42) (19) (42) 43 (39) (38) 11 2,000 .02775 57 (53) (49) (47) (14) (50) 49 (45) (43) + 2

1,500 .03700 63 (57) (52) (48) (+7) (54) 52 (46) (43) -8

1,110 .05000 71 (61) (55) (49) (-4) (60) 55 (48) (43) - 23

1,000 .05551 74 (63) (56) (50) (-10) (62) 56 (49) (43) -29

900 .0617 77 (64) (56) (50) (-15) (65) 56 (48) (42) -35

800 .0694 80 (66) (57) (51) (-22) (70) 57 (48) (42) -44

700 .0793 84 (67) (56) (49) (-32) (75) 56 (45) (38) -56

600 .0925 89 (68) (56) (47) (-43) (80) 56 (44) (35) -70

555.1 .1000 91 (68) (55) (45) (-52) (82) 55 (42) (32) -79

500 .1110 95 (69) (54) (44) (-62) (85) 54 (39) (29) -90

400 .1388 102 (69) (-92) (80) 50 -123

300 .1850 111 (65) (-137) 42 -173

277.5 .2000 113 (63) (-151) 38 -189

200 .2775 122 (56) (- 220) 22 -266

150 .3700 130 (44) (-303) + 1 -354

111.0 .5000 137 (24) (-413) -30 -463

100 .5551 140 (15) (-455) -45 -508

75 .7401 (-587) -91 -652

55.51 1.0000 (-760) -152 -831

50 1.1101 -178 *(-900)

40 1.3877 (- 1067)

*Estimated.

61
Table XVII. AH° at 25 °C

Investigator System

n, moles ILO/mole solute Original

temp of meas

No. of meas

- AHn,(T) -AHs,

(25 °C)

AHN, .(25 °C)

Acid Base Salt

°c cal/mole callmole cal/mole

Richards and Rowe [224] NaCl 100 100 201 16.80 5 14,059 ±15 13,687 13,364

15.67 4 14,114±8 13,689 13,366

KC1 100 100 201 16.77 3 14,157 ±10 13,763 13,372

15.63 4 14,218 ±10 13,768 13,377

NaN03 100 100 201 16.76 4 13,988 ±6 13,604 13,330

15.56 7 14,050 ±6 13,608 13,334

kno3 100 100 201 16.77 3 14,220 ±5 13,808 13,317

15.63 6 14,293 ±6 13,821 13,330

Gillespie, Lambert and Gibson NaCl 540 540 1081 20 1

! 13,773 13,516 13,349

[356] 283 283 567 20 1 13,793 13,545 13,333

550 550 1101 24.99 1 13,571 13,571 13,407

284 284 569 32.27 1 13,199 13,525 13,315

282.5 282.5 566 32.27 1 13,261 13,588 13,376

260 260 521 32.30 1 13,271 13,596 13,377

KC1 273.4 273.4 548 20 1 13,858 13,625 13,384

Bender and Biermann [213] NaCl 18.42 18.42 37.84 25 2 14,249 ±12 14,249 13,332

17.14 17.14 35.30 25 4 14,314± 10 14,314 13,331

Pitzer [206] NaCl 46.5 1065.5 1112 25 3 13,828 ±12 13,828 13,366

Vanderzee and Swanson [357] NaC104 5050 178.4 5261 25 2 13,465 ±15 13,465 13,332

188.6 4060.4 5160 25 6 13,398 ±5 13,398 13,337

62
Table XVIII. A//° of KCl(c) in H20 at 25 °C

Investigator Yearreported

Temp of measNo. of meas

Cone, range moles KC1/ lOOOg H20

AHl

°c cal/mole

1. Winkelmann [94] 1873 26-31 17 5.59 to 0.42 4,104 ±50

2. Berthelot [377] 1875 21 ? 0.28 3,970 ±150

3. von Rechenberg [381] 1879 16-20 7 .28 4,113 ±100

[382] 1880 17-20 7 .28 4,200 ±100

4. Berthelot and Ilosvay [383] 1883 18 ? .54 4,000 ±150

5. Thomsen [30] 1883 18 ? .28 4,107 ±50

6. Pickering [384] 1887 15-25 30 .28 4,143 ±50

7. von Stackelberg [275] 1898 18 3 4.44 to 0.55 4,110 ±100

8. Bronsted [385] 1906 25 4 0.46 to 0.09 4,167 ±20

9. Haigh [388] 1912 21 2 .14 4,081 ±50

10 Colson [350] 1915 18, 21 2 .17 4,184

11. Cohen, Helderman, and Moesveld [386] 1920 18 7 .28 4,070 ±30

12. Mees [387] 1920 18 2 .28 4,062

13. Mondain-Monval [268] 1923 18 1 .37 3,954

14. Sandonnini and Gerosa [141] 1925 18.5 4 .75 to 0.17 4,100 ±100

15. Wiist and Lange [21] 1925 25 12 4.47 to 0.37 4,157 ±40

16. Lange and Durr [389] 1926 25 10 0.56 4,147 ±40

17. Holluta and Werner [390] 1927 18.5, 20 2 .27 4,183 ±50

18. Cohen and Kooy [391] 1928 20 5 .28 4,110 ±10

25 3 .28 4,110 ±5

19. Chipman, Johnson, and Maass [133] 1929 15-27 16 .66 to 0.07 4,100 ±100

20. Partington and Soper [334] 1929 25 12 3.55 to 0.31 4,160 ±20

21. Roth and Eymann [392] 1929 21 8 0.37 4,112 ±15

22. Lange and Rounsefell [393] 1930 25 6 .28 4,116 ±10

23. Mishchenko [303] 1930 25 6 .25 4,114 ±10

24. Popov, Bundel, and Choller [165] 1930 20 10 .19 4,082 ± 25

25. Moles and Perez-Vitoria [394] 1932 20.5 1 .34 4,298

26. Smeets [395] 1933 20 3 .34 4,107 ±20

27. Popov, Khomyakov, Feodos’ev, and Schirokich [166] 1933 20 10 .19 4,077 ± 20

21 8 .28 4,115 ±10

23 19 .28 4,114 ±15

28. Drucker [45] 1935 17-23 12 .56 to 0.11 4,095 ± 35

29. Shibata and Terasaki [396] 1936 25 10 .15 to 0.07 4,164 ±20

30. Fedorov and Sil’chenko [271] 1937 20 3 .56 to 0.14 4,150 ±100

31. Lange and Martin [397] 1937 25 1 .13 4,147

32. Fontell [398] 1938 22.5 4 .06 to 0.01 4,124 ±10

25 6 4,117 ±15

33. Popov, Skuratov, and Strel’tsova [172] 1940 20 ? .28 4,125 ±20

34. Slansky [399] 1940 25 ? ?

a 4,075 ±40

35. Voskresenskaya and Ponomareva [400] 1946 25 9 6.18 4,124 ±20

36. Tichelaar [401] 1946 25 6 .02? 4,146 ±40

37. Foz and Colomina [402] 1946 25 1 .37 0 4,115 ±10

[403] 5 4,098 ±20

38. Fineman and Wallace [404] 1948 25 ? ?

a 4,113

39, Mishchenko and Kaganovich [405] 1949 25 6 6.28 4, 1 15 ± 10

40. Barieau and Giauque [406] 1950 25 3 .18 4,113 ±10

41. Samoilov [407, 408] 1951 25 1 .06 4,169

42. Kaganovich and Mishchenko [409] 1952 25 9 .26 4,117 ±10

43. Evans and Richards [410] 1952 25 4 .01 4,121 ±10

44. Kapustinskii and Drakin [411] 1952 25 ? .001 4,077 ±25

45. Spedding and Miller [412] 1952 25 6 .19 to 0.03 4,132 ±15

46. Voskresenskaya and Patsukova [413] 1952 25 ? .12 4,114 ±15

47. Westrum and Eyring [414] 1952 25 ? .02 4,109 ±15

48. Davies, Singer, and Stavely [368] 1954 25 5 .32 4,108 ±10

49. Hutchinson, Manchester, and Winslow [415] 1954 25 8 .28, 0.03 4,120 ±8

50. Chernyaev, Sokolov, and Palkin [416] 1954 25 3 .02 4,129 ±15

51. Hutchinson and White [417] 1955 25 4 .01 to 0.007 4,120 ±25

52. Higgins [418] 1955 25 3 .11 4,133 ±10

Footnotes at end of table. 63
Table XVIII. A//° of KCl(c) in H2 O at 25 °C — Continued

Investigator Yearreported

Temp of meas

No. of meas

Cone, range moles KC1

lOOOg H2 0

AH°x

°C cal/mole

53. Papadopoulos and Giauque [419] 1955 25 3 0.28 4,107 ±6

54. Coops, Balk, and Tolk [420] 1956 25 16 .01 4,082 ± 20

55. Gunn [421] 1958 25 8 .28 4,122 ±2

56. Balk and Benson [422] 1959 25 9 .20 4,125 ±5

57. Sacconi, Paoletti, and Ciampolini [205, 423] 1959 25 10 .33 4,119 ±10

58. Sunner and Wadso [424] 1959 25 11 .12 4,100 ±5

59. Bills and Cotton [425] 1960 25 4 .28 4,121 ±10

60. Hietala [426] 1960 25 3 .28 4,116 ±10

61. Gallagher and King [427] 1960 25 14 .14-0.7 4,120 ±10

62. Dekker [428] 1961 25 ? .28 4,109:4,106

63. Reshetnikov [429] 1961 25 6 .19 to 0.11 4,112 ±10

64. Ciampolini and Paoletti [430] 1961 25 8 .33 4,118 ±10

65. Higgins and Westrum [431] 1961 25 3 .11 4,133 ±10

66. Argue, Mercer, and Cobble [432] 1961 25 4 .005 4,117 ±10

67. Coops, Somsen, and Tolk [433] 1961 25 10 .02 to 0.007 4,109 ±5

1959 10 4,106 ±5

1958 4 4,107 ±8

1957 5

c 4,105 ±10

1957 6

c 4,107 ±10

68. Busey, Dearman, and Bevan [434] 1962 25 ? .10 4,117 ±10

69. Newman [435] 1962 25 12 .04 4,124 ±10

70. Talakin et al., [436] 1962 25 3 .19 4.088 ± 25

a Authors’ extrapolation.

b Foz and Colomina report this as their best value.

‘ Measurements made'by Tolk in apparatus of Coops, Balk and Tolk.

Table XIX. A//° of NaCl in H2 0 at 25 °C

Investigator

Year

reported

Temp of meas

No. of meas

Cone, range moles NaCl/

lOOOg H2 0

AHI

°C cal/mole

1. Winkelmann [94] 1873 16-30 20 5.50 to 0.53 914 ±30

2. Ostwald [443] 1882 16-17 4 0.19 970

3. Thomsen [30] 1883 16.8 2 .56 897 ±20

4. Pickering [384] 1887 15-25 35 .28 935 ±20

5. Colson [535] 1915 21 1 .42 894

6. Randall and Bisson [143] 1920 25 7 .54 to 0.13 929 ±5

7. Wiist and Lange [21] 1925 25 14 5.62 to 0.52 a 931 ±10

8. Lange and Durr [389] 1926 25 10 0.56 841

9. Lipsett, Johnson, and Maass [323] 1927 25 20 5.50 to 0.07 923 ±5

[536] 1927 20 15 5.92 to 0.04 922 ±8

10. Cohen and Kooy [391] 1928 25 4 0.56 915 ±5

20 5 .56 921 ±8

11. Askew, Bullock, Smith, Tinkler, Gatty, and Wolfenden [499] 1934 20 9 .03 904 ±30

12. Becker and Roth [228] 1935 19.7 5 .09 to 0.04 918 ±10

13. Lange and Martin [397] 1937 25 1 .25 934

14. Slansky [399] 1940 25 ? ? a 915 ±10

15. Tichelaar [401] 1946 25 5 0.02? 950 ±30

16. Voskresenskaya and Ponomareva [400] 1946 25 ? .37 970

17. Fineman and Wallace [404] 1948 25 ? ? a 925 ±5

18. Samoilov [407, 408] 1951 25 i 0.19 932

19. Kapustinskii and Drakin [411] 1952 25 1 .0008 932 ±30

20. Seki and Suzuki [537] 1953 18 ? .14 913 ±20

21. Benson and Benson [324] 1955 25 16 1.3 to 0.05 928 ±3

22. Benson, Goddard, and Hoeve [538] 1956 25 3 0.50 927 ±3

23. Attree, Cushing, Ladd, and Pieroni [539] 1958 25 ? .01 927 ±10

24. Lister and Myers [540] 1958 25 ? .18 914 ±10

25. Samoilov and Buslaeva [444] 1960 15, 35 2 .14 874 ±100

26. Criss and Cobble [541] 1961 25 17 .02 to 0.001 914 ±10

Authors’ extrapolation.

64
Table XX. AH° of KN03 in H2 0 at 25 °C

Investigator Year

reported

Temp of meas

No. of meas

Cone, range moles KNO3/ lOOOg H2 0

ah:

1. Winkelmann [94] 1873 °C

27-29 14 2.41 to 0.31 cal/mole

8,350 ± 50

2. Thomsen [30] 1883 18 3 0.28 8,300 ± 50

3. Tilden [560] 1884 15, 34 4 .56 8,295 ± 100

4. Pickering [384] 1887 15-25 27 .28 8,430 ± 75

5. von Stackelberg [275] 1898 15 10 2.44 to 0.22 8,361 ±50

6. Haigh [388] 1912 21 3 0.14 8,240 ± 75

7. Mondain-Monval [267] 1925 16.9 1 .20 8,200

8. Berenger-Calvet [351] 1927 14-16 30 2.49 to 0.09 8,355 ±40

9. Holluta and Werner [390] 1927 18.5 1 0.16 8,592

10. Roth [576] 1927 20.5 6 .16 8,455

11. Roth and Muller [577] 1927 20.5 3 .16 8,304

12. Roth and Eymann [392]; Roth [578] 1929 21 4 .16 8,372 ± 20

13. Cohen and Kooy [391] 1928 20, 20.5 6 .28, 0.16 8,373 ± 20

14. Nacken [477] 1930 20? 2 .27 8,585

15. Lange and Monheim [173] 1930 25 5 .07 to 0.05 8,375 ±40

16. Drucker [45] 1934 18.1 1 .23 8,285

17. Fedorov and Sil’chenko [271] 1937 22 3 .56 to 0.14 8,380 ± 75

18. Hieber and Feder [579] 1938 20 1 .16 8,340

19. Hiickel, Datow, and Simmersbach [580] 1940 18.5 3 .12 8,407 ±40

20. Voskresenskaya and Ponomareva [581] 1944 25 1 .18 8,298

21. Voskresenskaya and Ponomareva [400] 1946 25 1 .18 8,290

22. Westrum and Eyring [414] 1952 25 4 .01 8,325 ± 20

23. Lipilina and Samoilov [582] 1954 25 1 1.11 9,320

24. Bills and Cotton [425] 1960 25 3 0.14 8,400 ± 40

25. Turnbull [583] 1961 25 1 .11 8,600 ± 100
Table XXI. Heat of Solution

A//°, 25 °C for uni-univalent electrolytes in H2O

Substance State AHI Substance State AH° Substance State AHI

callmole cal/mole cal/mole

HF g - 14,700 LiBr-2H2 0 c - 2,250 KC1 c 4,115

HC1 g -17,888 LiBrC>3 c 340 KCIO3 c 9,890

HC104 1 -21,215 Lil c -15,130 KCIO4 c 12,200

HC104 H2 0 c -7,875 LiIH2 0 c - 7,090 KBr c 4,750

HBr g -20,350 LiI-2H2 0 c -3,530 KBr03 c 9,830

HI g - 19,520 LiI-3H2 0 c 140 KI c 4,860

HI03 c 2,100 LiN02 c - 2,630 KIO3 c 6,630

HN03 1 -7,954 LiN02 -H2 0 c 1,680 kno2 c 3,190

HCOOH 1 -205 LiN03 c -600 KNO3 c 8,340

CH3 COOH 1 -360 kc2 h3 o2 c -3,665

NaOH c - 10,637 KCN c 2,800

nh3 g -7,290 NaOHH2 0 c -5,118 KCNO c 4,840

NH4 CI c 3,533 NaF c 218 KCNS c 5,790

NH4 CIO4 c 8,000 NaCl c 928 KMn04 c 10,410

NH4 Br c 4,010 NaC102 c 80

NH4 I c 3,280 NaC102 -3H20 c 6,830 RbOH c - 14,900

NH4 IO3 c 7,600 NaC103 c 5,191 RbOHH2 0 c -4,310

NH4 NO2 c 4,600 NaC104 c 3,317 Rb0H-2H2 0 c 210

nh4no3 c 6,140 NaC104 H2 0 c 5,380 RbF c -6,240

NH4 C2 H302 c -570 NaBr c -144 RbF-H2 0 c -100

NH4 CN c 4,200 NaBr-2H2 0 c 4,454 RbFl |H2 0 c 320

NH4 CNS c 5,400 NaBrOs c 6,430 RbCl c 4,130

CH3 NH3 CI c 1,378 Nal c - 1,800 RbC103 c 11,410

(CH3 ) 3NHC1 c 350 NaI-2H2 0 c 3,855 RbC104 c 13,560

N(CH3) 4C1 c 975 NaI03 c 4,850 RbBr c 5,230

N(CH3)4Br c 5,800 NaN02 c 3,320 RbBr03 c 11,700

N(CH3) 4I c 10,055 NaNOa c 4,900 Rbl c 6,000

NaC2 H3 02 c -4,140 RbN03 c 8,720

AgC104 c 1,760 NaC2H302 , 3H2 0 c 4,700

AgN02 c 8,830 NaCN c 290 CsOH c -17,100

AgNOs c 5,400 NaCN- |H2 0 c 790 CsOHH2 0 c -4,900

NaCN-2H2 0 c 4,440 CsF c -8,810

LiOH c -5,632 NaCNO c 4,590 CsFH2 0 c -2,500

LiOH-H2 0 c -1,600 NaCNS c 1,632 CsF-1|H2 0 c - 1,300

LiF c 1,130 CsCl c 4,250

LiCl c -8,850 KOH c -13,769 CsC104 c 13,250

LiClH2 0 c -4,560 kohh2 o c -3,500 CsBr c 6,210

LiC104 c - 6,345 KOH-l|H2 0 c -2,500 CsBrOs c 12,060

LiC104 -3H2 0 c 7,795 KF c -4,238 Csl c 7,970

LiBr c -11,670 KF-2H2 0 c 1,666 CsNOa c 9,560

LiBrH2 0 c -5,560

66

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