(MIST

PUBLICATIONS

REFERENCE

NAT'L INST. OF STAND & TECH

AlllQt. MM15MS

NBSIR 86-3487

Technical Activities 1986

Chemical Thermodynamics Division

S. Abramowitz, Chief

U.S. DEPARTMENT OF COMMERCE

National Bureau of Standards

National Measurement Labroatory

Center for Chemical Physics

Chemical Thermodynamics Division

Gaithersburg, MD 20899

November 1986

Preoared for: QC EPARTMENT OF COMMERCE

/ ^ ^ lal Bureau of Standards

~ Li 5 irsburg, MD 20899

/tat

NBSIR 86-3487

TECHNICAL ACTIVITIES 1986

CHEMICAL THERMODYNAMICS DIVISION

S. Abramowitz, Chief

U.S. DEPARTMENT OF COMMERCE

National Bureau of Standards

National Measurement Labroatory

Center for Chemical Physics

Chemical Thermodynamics Division

Gaithersburg, MD 20899

November 1986

Prepared for: U.S. DEPARTMENT OF COMMERCE

National Bureau of Standards

Gaithersburg, MD 20899

U.S. DEPARTMENT OF COMMERCE, Malcolm Baldrige, Secretary

NATIONAL BUREAU OF STANDARDS, Ernest Ambler, Director
, • t , V

' > i

'!* iT.'ki ,

V}‘\ \

lalrtO': iJ8<l!i(S<^ifc'.8^

sis*-;;!'^"

ioamro w

^ iissei0H,_

- V^'5v3i!iJ ‘

; r«!

3DR3MMCX) 10

afciffbjijsts to Mm“tiM ': " ^W8 CM

I

.Bt^nmu(^p no w,as?4w

'"

{((ft-
ABSTRACT

This report summarizes the technical activities of the NBS Chemical

Thermodynamics Division during the Fiscal Year 1986. The activities of the

Division include research on: thermodynamic properties of enzyme - catalyzed

reactions, DSC standards for biological systems, computer modeling of phase

transitions of biomolecules, determination of the structure of proteins and

nucleic acids using x-ray and neutron diffraction, combustion bomb calorimetry

of pure substances, mass balances of chlorine during combustion processes,

high temperature heat capacity measurements, evaluation of the thermochemistry

of calcium and iron compounds, preparation of JANAF Thermochemical Tables, and

automation of Data Center procedures, A listing is provided of publications

and talks given by the Division staff.

iii
sr

' 7

. '’'r.'-'k. •fj.-," ''-^.--'‘i^r' 'v; 1'"^.

'

. ; --''I

.

• • '

. -

' ity

- • ,.

' -. ,;•

V " • -''• '

-i’S' rf-'UZf 7o ,, 3'

•

. ^

'

- •i "^^"‘

'l''

' "' - '

I •

br..4 e'fJ'j ?V> »|

' V

^ ’ ' ’ '-

.0>'>'-
Staff of the Chemical Thermodynamics Division

S. Abramowitz, Chief

B. Wiest, Secretary

Bio thermodynamics Biomolecular Structure

S. Abramowitz, Group Leader A. Wlodawer, Group Leader

E. Gajewski G. Gilliland

R. Goldberg R. Harrison 3 W. Kirchhoff M. Miller 1 T. O'Leary 1 J. Nachman 1 Y. Tewari H. Savage 7 F. Schwarz I. Weber

A. Shrake 1 D. Steckler 2

Thermodynamic Measurements Thermodynamic Data Centers

E.S. Domalski, Group Leader M. Chase, Group Leader

T. Buckley S. Aronson 2 M. Bruce 7 D. Bickham 5 M . Burns 2 J. Dill 2 K . Churney D. Garvin

J. Colbert P. Fagan 7 E. Diaz 6 E. Hearing 4

D. Ditmars C. Jackson

D. Kirklin T. Jobe

A. Ledford W. King

J . Rukkers 1 R. Nuttall 4

S . Sung 2 V. Parker

T. Celano 2 R. Schumm 4

D. Smith- Magowan

D. Wagman 1 S. Wasik 4

R. Wood 6 N. Young 4

1 Guest Worker

2 Summer Student

3 NRC Fellow

4 Contractor

5 Part-time

6 WAE

7 Transferred within NBS

V
!. IT .

‘ ir, .V ''Vi :-, j ,

;. r,

!mi

•a*o*V-'.t '>‘fC''f.'. . .-A

.u-xfci: 0.n*> •?>

t

- 1,4 '-i'H -it

i. uMjf':.4vi. -u

•' s ,..

i

- A'' s;,? H

:wd0'. '

2t,4 "i

'7v T'

'»

i!'>' 'J 1

>'> •a

^' {/*0 Jkt.

«.: r;ie‘"

-.•>

"•- d

rV

• i,> :» ;.: o-{^. /i

:i<» ’"xr

*->

V (•.•?/ :.St

„>", ;’ ,• J a

’ f/ iffijrisV a

•**

•4 %

ii
TABLE OF CONTENTS

Abstract iii

Staff of the Chemical Thermodynamic Division. v

1. Introduction 1

A. Obj ectives 1

B. Organization and Staff. . 2

2 . Biothermodynamics 5

A. Biochemical Thermodynamics 5

B. Differential Scanning Calorimetry. .9

3 . Biomolecular Structure ........................................... 15

A. Structural Studies of Mutations in Catabolite

Gene Activator Protein. . 15

B. Predicted Structure for Two Domains of the

Regulatory Subunit of cAMP- dependent Protein Kinase. ....16

C. Structural Studies of Anti- tumor Amidohydrolases 16

D. Comparison of Two High Resolution Structures of

Bovine Pancreatic Trypsin Inhibitor 17

E. High Resolution Refinement of Ribonuclease A 18

F. Structure of the Solvent in Crystalline BPTI 19

G. Crystallization of Synthetic Fragments of DNA 20

H. Application of Repulsive Regularities Found in

Water Structures 20

I. Plans for Next Year 21

I

4. Chemical Thermodynamics Measurements

A. Large Sample Combustion Calorimetry 24

B. Calormetric Update on SRM Coals 2682,

2683, 2684 and 2685 28

C. Bomb Calorimetric Measurements for Biotechnology 29

D. Estimation Methods and Combustion Calorimetry

vii
of Organic Phosphorus Compounds 29

E. Drop Calorimetry of Non-Reacting Systems

Below 2800 K . 32

5 . Chemical Thermodynamics Data Activities 35

A. Chemical Thermodynamics Data 36

B . Electrolyte Data 45

C. Thermodynamic Properties of Organic Compounds 50

D. Automating Data Center Procedures. 51

6. Publications... 54

7. Talks 60

8. Chemical Thermodynamics Division Seminars 64

9. Technical and Professional Committee

Paricipation and Leadership 66

10. Professional Interactions, Consulting and

Advisory Services 68

11. Visiting Scientists 75

viii
CHEMICAL THERMODYNAMICS DIVISION

S. Abramowitz, Chief

SUMMARY OF ACTIVITIES

Fiscal Year 1986

1 . INTRODUCTION

A. Objectives

Chemical Thermodynamics provides measurement techniques, concepts and

data on the energetics and equilibria of chemical processes. Chemical

thermodynamics is used to predict equilibria in chemical reactions,

thermodynamic properties of high temperature refractory materials and gases,

activities of aqueous solutions used in technologies varying from power

generation and electrorefining to biotechnology. This division develops the

models necessary for correlating structure with thermodynamic properties,

develops the science of calorimetry in order to obtain precise data from

the microwatt to megawatt levels, carries out precise thermodynamic

measurements, including those on Standard Reference Materials, develops

the measurement capabilities for molecular structure determinations and

critically evaluates thermodynamic data in all phases for the use of

industry, government and academia. A current emphasis is directed towards

the needs of the emerging biotechnology industry. In particular, this

division is developing the measurement and computational techniques for

obtaining biomolecular structures of proteins, enzymes, enzyme-substrate

complexes and DNA species using x-ray and neutron diffraction. The

thermochemistry of generic processes of interest to biochemistry and

biotechnology are being studied in order to develop standards and provide

key data, to develop quantitative models for the energetics of these

processes and estimation schemes of demonstrated reliability for the

concomitant thermodynamic properties. A new effort is being launched in the

coming year aimed at correlating structure and function for proteins.

This research will coordinate with the biothermodynamics and biomolecular

structure efforts in order to develop structure-function-energetics

correlations.

The objectives of the Chemical Thermodynamics Division include:

o Application of the science of calorimetry to the needs of

existing and new technologies through the design of novel

calorimeters and the development of improved procedures to obtain

enhanced measurement precision and accuracy.

o Development and certification of Standard Reference Materials for the use of existing and emerging technologies.

o Measurement of the thermochemical properties of key chemical species

and processes including bioprocesses and phase transitions of aqueous

biomolecular species.

1
o Provision of critically evaluated compilations of the thermodynamic

properties of inorganic , organic and bioorganic compounds in the

gaseous, liquid, solid and aqueous phases.

o Development of estimation schemes for the prediction of thermodynamic

properties of organic, inorganic, and bioorganic species in the

gaseous, liquid, solid and aqueous phases.

o Development of measurement and computational methodology for the

determination of the structure of biomacromolecular species using the

techniques of x-ray and neutron diffraction.

In achieving these objectives Division scientists are encouraged to be aware of and to respond to the needs of industry, government and academic

institutions for measurement standards, accurate data and concepts in the

field of thermodynamics.

B. Organization and Staff

The Chemical Thermodynamics Division has four groups. An additional

group has been organized, this year, under the leadership of Alex Wlodawer

to guide the growth in the biomolecular structure group. Malcolm Chase

has assumed the leadership of the Chemical Thermodynamic Data Centers

Group, which includes the Chemical Thermodynamics Data Center and

Electrolyte Data Center. Dr. Chase has extensive industrial experience in

the evaluation of chemical thermodynamic data for both industrial and

military technologies. He brings to this position an awareness of the

needs of these technologies and will make the products of this group more responsive to those needs. Dr. Chase will also continue his activity as

the director of the JANAF Thermochemical Data Project. This change in

leadership will allow David Garvin to devote all his energies to the

evaluation of chemical thermodynamic data in support of national and

international data evaluation programs. The group structure is

o Biothermodynamics, S. Abramowitz, Group Leader

o Biomolecular Structure, A. Wlodawer, Group Leader

o Chemical Thermodynamics Measurements, E.S. Domalski, Group Leader

o Chemical Thermodynamic Data Centers, M.W. Chase, Group Leader

The division has 26 full-time staff, 1 part-time employee, 6 guest

workers, 7 students, 5 contractors and 1 consultant. This fiscal year two

additional members have joined the Biomolecular Structure Group. Dr.

Gilliland will be continuing work he began elsewhere on the maintenance

and development of a computer based database for the crystallization of

biomolecular species and will conduct research in biomacromolecular

structure and on means to systemize the crystallization of proteins and

other biomolecular species. Dr. Weber will conduct research on evaluating

the effects of selected mutations on the structures of proteins and

protein-substrate complexes. In addition the group has a postdoctoral

associate, three guest workers and a technician. Funas for one guest

worker and the technician are being provided by the Center for Advanced

2
Research in Biotechnology (CARB) to support research of mutual interest.

This group has acquired state-of-the-art computing and x-ray detector

equipment in the last year. It also has access to additional equipment

through its collaboration with others including CARB and Cenex.

Additional expansion is planned for FY87 in the area of protein

structure-function studies. A laboratory will be refurbished for

molecular biology work and will be used for protein synthesis and for the

investigation of the effect of changes in protein structure on function.

It is expected that this new activity will involve close collaboration

with the biothermodynamics and biomolecular structure programs.

The division participates in the work of the Office of Standard

Reference Data and the Office of Standard Reference Materials. In support

of the Standard Reference Data program, the Chemical Thermodynamics Data

Centers group evaluates thermochemical data for organic and inorganic

species, develops database management systems for chemical thermodynamics,

and develops critically evaluated data and reliable estimation schemes for

organic and biochemical species. In support of the Standard Reference

Materials program, the Thermodynamics Measurements Group maintains standards for

oxygen bomb and heat capacity calorimetry and develops new standards as needed. Benzoic acid is a best seller of the Standard Reference Material

Program. It is responsible for converting the chemical system of

measurements to the electrical system and is used to calibrate combustion

bomb calorimeters for the fuel industry, power generation industry and in

bomb calorimeter research laboratories.

The research needs of two federal agencies and one industrial trade

association are being addressed by the division. We receive funding from

the Department of Energy for determining the chlorine content of municipal

solid waste and optimizing conditions for the formation and destruction of

chlorinated organic species, and for the development of thermodynamic data

for flue gas clean-up in fossil fuel technology. Programs being pursued

for the Department of Defense include the provision of combustion

calorimetric data and estimation methods for the thermodynamic and related

properties of organic phosphorus compounds and development of

thermodynamic functions for species of importance to high temperature

technologies including rocketry, reentry, and energy production. We are developing computer algorithms for aqueous thermodynamics and providing

annotated bibliographies for the sources of the data for the Design

Institute for Physical Property Data (DIPPR), which is sponsored by AIChE.

We have finished the revision of a previous publication on the

thermodynamic data for biomass and waste incineration in cooperation with

the Solar Energy Research Institute (SERI).

In addition to the interactions which we have with other NBS programs

and federal agencies the division cooperates with other NBS units. Within

COP we have a joint program with the Chemical Kinetics Division on database managment systems, with both the Chemical Kinetics

and Spectroscopy Divisions in developing and carrying out a research

program in support of the high temperature tecnnology needs of AFOSR and

with the Surface Science Division in developing computer algorithms for

the interpretation of sputtering depth profiles.

3
Within NML we are cooperating with the Center for Analytical

Chemistry on several programs in the area of biotechnology including the

thermodynamics characterization of monoclonal antibody antigen

interactions and the use of NMR in speciating carbohydrates. We are also

collaborating with the Center for Basic Standards on temperature

measurements in combustion studies. We are cooperating in the planning

and carrying out of a research program in support of AFOSR needs in

cooperation with both IMSE and NEL.

Our staff has many interactions with voluntary standards

organizations and international societies such as ASTM, ANSI, ASME,

CODATA, lUPAC, and IAEA etc. This past year staff members participated in

the planning and formations of a new ASTM committee on Biotechnology,

Staff members hold memberships on diverse committees ranging from

environmental and health concerns to energy utilization and database

management. Members of the Biomolecular Structure Group organized a three-day Mid-Atlantic Protein Cystallography Workshop at NBS in May 1986.

The workshop was attended by about 80 scientists.

We are actively planning for the maintenance of a protein

crystallization database. Computing expertise for the necessary

programming for this task will be provided by the Chemical Thermodynamics

Data Centers Group. The differential scanning calorimetry effort has been

successfully integrated into the biothermodynamics efforts in this past

year. This laboratory is documenting standard procedures for calibrating

differential scanning calorimeters that have been designed for use with

biochemical samples. Work has continued in the measurement of the

thermodynamics of enzyme catalyzed reactions. The work on the five and

six membered monosaccharides has been completed and efforts will be made,

in the coming year, to construct estimation schemes for the prediction of

the thermodynamic formation properties for this class of compounds.

Efforts have begun in other areas including the measurement of the

thermodynamics of the reactions of monoclonal antibodies with antigens and

the use of microcalorimetry to characterize the rates of enzyme catalyzed

reactions and to measure enzyme activity.

Work will also continue on the determination of enthalpies of

formation of key phosphorus compounds and other biomolecular building

blocks including the development of predictive schemes for these

compounds. Benzoic acid will be recertified during this fiscal year.

Research to characterize the chlorinated organic species present in the

effluents resulting from the combustion of municipal solid waste will also

be continued.

4
2. BIOTHERMODYNAMICS

S. Abramowitz, E. Gajewski, R.N. Goldberg, W.H. Kirchhoff,

F.P. Schwarz, D. Sleekier, Y.B. Tewari

A. Biochemical Thermodynamics

(R.N. Goldberg, E. Gajewski, D. Sleekier, Y.B. Tewari)

The long lerm goals of Ihis research are lo provide underslanding of

Ihe Ihermodynamics of Ihe key processes and inleraclions relevanl lo

biochemislry and biolechnology . This underslanding is needed lo predicl

Ihe feasibilily of biochemical processes, oplimizalion of producl yields

and eliminalion of side reaclions in induslrial processes. The dala are necessary lo conslrucl eslimalion schemes lo reliably predicl Ihe Ihermochemical

properlies of subslances and processes for which measuremenls are noi

available. The goals are realized by developmenl of measuremenl and

compulalional melhodology, delerminalion of reliable Ihermodynamic values,

and eslabl ishmenl of ihe relalionship belween molecular slruclure and Ihe

formulalion of prediciive melhods.

The Ihermodynamic invesligalions include, where feasible, bolh

equilibrium composilion and calorimelric measuremenls on carefully

characler ized biochemical syslems. Independenl measuremenls of enlhalpy

and equilibrium composilion as a funclion of lemperalure enable Ihe

reliable modelling of reaclions oulside of Ihe lemperalure range of Ihe

measuremenls. The effecls of pH, melal ion concenlralion , ionic slrenglh

and lemperalure on Ihe equilibrium and enlhalpy measuremenls are also

invesligaled. An equilibrium model of Ihe syslem allows one lo accounl

for Ihe exper imenlally delermined values and lo predicl ihese quanlilies

under a variely of possible condilions. The calculalions require

idenlif icalion of Ihe individual molecular processes, aclivily coefficienl

models lo accounl for nonidealily, and numerical solulion of Ihe

equilibrium equalions which describe Ihe- syslem. The final sel of

Ihermodynamic paramelers makes possible Ihe prediclion of Ihe

Ihermodynamic behavior of a syslem under a wide range of condilions beyond

Ihose used for Ihe measuremenls. The combined approaches of equilibrium

measuremenls, calorimelry and compuler modelling is believed lo be unique

lo NBS.

Wrillen descriplions of Ihe microcalorimelers , procedures and

soflware used in Ihe sludies of biochemical syslems have been prepared.

The documenlalion includes a delailed descriplion of Ihe conslruclion

,

calibralion, operalion, performance and use of Ihese calorimelers . The

soflware allows for Ihe acquisilion and Irealmenl of dala from Ihree

microcalorimelers simullaneously . Soflware for Ihe acquisilion and

Irealmenl of dala from an isoperibol solulion calorimeler, using a quarlz

Ihermomeler, is also described. Procedures for oblaining kinelic

paramelers such as enzyme aclivily and rales of conversion of subslrale lo

producl are also described wilh accompanying examples using glucose

isomerase

.

Summaries of Ihe accomplishmenls of Ihe individual projecls follow:

5
1. Thermodynamics of the Hydrolysis of Adenosine 5 ’ “Triphosphate

The enthalpy of the hydrolysis of the enzyme catalyzed conversion of

adenosine 5 ’ “triphosphate (ATP) to adenosine 5 ’ “diphosphate (ADP) and

inorganic phosphate was investigated using microcalorimetry. There are five measurements of this equilibrium in the literature. Four of these

are in agreement. All of them involve the use of coupled reactions to

obtain the Gibbs energy change, which is known to ± 1.5 kJ mol“'' . These

results are sufficiently accurate for our needs. Enthalpies of reaction

were measured as a function of ionic strength (0.05 to 0,66 mol kg~^ ) , pH

(6.4 to 8.8) and temperature (25 to 37 °C) in Tris/HCl buffer. The

measured enthalpies were adjusted for the effects of proton ionization

and metal ion binding, protonation, interaction with the Tris buffer and

ionic strength effects to obtain a value of AH = -20.5 ± 0.4 kJ mol“^ at

25 °C for the process:

ATP^“ + H

2 O = ADP3" + HPOij" + H""

Since earlier investigations did not systematically investigate the

effects of pH, ionic strength or temperature the results obtained are currently the best value for the enthalpy change for this biochemical

process. The result of ACp® = -237 ± 30 J mol“^ K“^ is the only

direct determination of this thermodynamic quantity.

2. Thermodynamics of Carbohydrate Isomerization Reactions

The thermodynamics of the enzymatic conversion of aqueous D-psicose to

D-allose was investigated using high pressure liquid chromatography. The

reaction was carried out in phosphate buffer at pH 7.4 over the temperature of 44,1 to 76.1 °C. From the temperature dependency of the equilibrium constants, the following results were ' obtained for the conversion

process at 25 C: AG° = -1.4l ± 0.09 kJ mol“^ , AH° = 7.42 ± 1.7 kJ mol"”* and

ACp° was estimated to be 67 ±. 50 J mol“"'K“^. An approximate equilibrium

constant of 0.3 was also obtained at 60 °C for the conversion of D-psicose

to D-altrose. The kinetics of these reactions are not rapid enough to

permit a direct calorimetric determination of the enthalpy changes.

This study is a continuation of earlier studies of carbohydrate

isomerization reactions using the enzyme, glucose isomerase, which included

isomerizations of glucose to fructose, xylose to xylulose and ribose to

ribulose and arabinose. The possibility of other isomerization reactions

involving sorbose, galactose, tagatose and talose were also investigated.

Isomerization was not observed for the above carbohydrates.

The available information on the thermodynamics of the aldo/keto

isomerization of hexoses and pentose is summarized in Table 1 . With the

exception of the mannose/fructose system, all the results were determined

in this laboratory using both HPLC, for the determination of equilibrium

constants, and where feasible, microcalorimetry to determine both the

enthalphy and heat capacity changes. This represents the most complete

set of information on the thermodynamics of carbohydrate isomerization

reactions

6
The observed thermodynamic data for the hexoses and pentoses will be

coupled with other thermodynamic data such as enthalpies of combustion and

solution and heat capacities to estimate the thermodynamic formation

properties of the hexoses and pentoses. Available NMR and polarimeteric

data will be used, where appropriate, to obtain speciation information for

the solutions.

Table 1

Thermodynamics of isomerization reactions involving D-aldohexoses and

D-aldopentoses in aqueous solution 298. 15K

Process AGO AHO ASO o

Q.

<1 O

(kJ mol“^

)

(kJ mol*"^ ) (J mol"'' K“l) (J mol“^ K"'

Ribose-arabinose -3.44±0.30 -9.8±3.0^ -21 .3

Ribose-ribulose 2.85±0. 1

4

1 1 c0±1 .5^ 27.3

Xylose-xylulose 4.38g±0.031 16.09±0.67^ 39.2 40±23^

Arabinose-ribulose 6.29±0.34 20. 75 ±3. 4^ 48.5

Allose-psicose -1 .41 ±0.09 7.42±1 .7^ 29.6 67+50'^

Psicose-altrose =3.4

Allose-altrose =2.0

Glucose-fructose 0.349±0.053 2.78±0.200 8.15 76±300

Mannose- fructose -2.72 0.0^ 9.12

Glucose-mannose 3.07 2.78 +0.97

^ Based on direct calorimetric measurements.

Calculated from the temperature dependency of equilibrium constants.

^ Calculated from the temperature depenaency of enthalpies of reaction.

^ Based on both an estimate and the temperature dependency of equilibrium

constants

.

3. Equilibrium Studies of the Conversion of Trans-Cinnamic Acid and

Ammonia to L-Phenylalanine

The thermodynamics of the enzymatic conversion of aqueous

trans-cinnamic acid and ammonia to L-phenylalanine has been investigated

using high pressure liquid chromatography. The reaction was carried out

in 0.1 M Tris/HCl buffer containing ammonium chloride over the pH range 7.0

to 7.7, at ionic strengths from 1.0 to 2.1 mol kg“^ in the temperature

range of 12 to 43 °C. Analysis of the HPLC data using an estimated heat

capacity change of 50 kJ mol”^ and an ion size parameter of 1.6

mol~^^^ kg“^^^ leads to an equilibrium constant of 0.86 ± 0.22 at 25 °C

for the process

Trans-cinnamic“ acid + = L-PhenylalanineWe were unable to bring about a sufficiently rapid reaction to permit a direct calorimetric measurement of the enthalpy of this reaction. The use

of these thermodynamic parameters in an equilibrium model allows for the

7
prediction of values of the apparent equilibrium constant as a function of

pH, temperature and composition. These data are useful for optimizing the

yield of phenylalanine. The available thermochemical data for this

generic type of reaction (ammonia elimination and the formation of a double bond) can be rationalized in terms of a scheme which views the

entropy changes for related processes to be comparable and then attributes

differences in Gibbs energy changes to the enthalpy changes which can be

influenced by resonance stabilization of the double bond which is formed.

This study complements an earlier one on the conversion of fumaric acid

and ammonia to aspartic acid.

Microcalorimetric Measurement of Enzyme Activity

In addition to thermodynamic studies, the- microcalorimetric

instrumentation can be used for the determination of enzyme activity. If

the substrate is present in large excess relative to enzyme, the reaction

will be slow and accompanied by a steady rate of heat production per unit

time given by

dq/dt = (dn/dt)/AH

where AH is the molar enthalpy of reaction and (dn/dt) is the number of

moles of substrate converted per unit time. The quantity (dn/dt) is a measure of the enzyme activity and can be determined from the measured

power (dq/dt) if the enthalpy of reaction is known. This technique may

prove valuable for the measurement of the activity of creatine kinase.

Currently, the activity of this enzyme is measured spectrophotometrically

with a precision of about 16)S. The procedure requires the coupling of

three enzyme catalyzed reactions to produce an increase of absorbance at

3^0 nm. A single step process can be used to measure this process in a microcalorimeter

Creatine Phosphate + ADP = Creatine + ATP

Results obtained have confirmed the literature results for the enthalpy of

this reaction. Also the measurement of enzyme activity in aqueous buffer

solutions have yielded results having an imprecision less than 10%.

Measurements of this activity in human serum will require steps to

eliminate and/or correct for possible chemical interferences in the

measurements

5. The Hydrolysis of Glucose 6-Phosphate and Fructose 6-Phosphate and

the Isomerization of Glucose 6-Phosphate to Fructose 6-Phosphate.

G6P“2 = G + HP0ij2

F6P“2 = f + HP On

2

G6P“2 = f6P“2

Here glucose and fructose are abbreviated as, G and F,

respectively. The aim of this research is to obtain enthalpy, heat

capacity and Gibbs energy changes for these processes. The results will

be examined in conjunction with the thermodynamic data obtained previously

for the hydrolysis of ATP of glucose and fructose, and the phosphorylation

of glucose and fructose by ATP.

8
To date, enthalpy measurements have been made on the first two

processes as a function of pH, temperature and concentration of magnesium

chloride and of Tris/HCl buffer. A preliminary set of measurements have been

made on the third process. After completion of the measurements on the

third reaction, the necessary corrections will be made to obtain the

enthalpy changes and the formalism applied to the Krebs cycle will be used

to obtain the best consistent set of thermodynamic parameters for the above

reactions, phosphorylation of glucose and fructose by ATP, and hydrolysis

of ATP.

6. Antigen-Antibody Interactions

A study of antigen-antibody reactions has been started, in

cooperation with the Center for Analytical Chemistry, using monoclonal

antibodies. This should aid in the molecular interpretation of the

thermodynamic properties of the reaction. A sample of a monoclonal antibody, has been obtained. The antibody has a molecular weight of about

150,000 dal tons and is specific for E-N-E dinitrophenyl-L-lysine (2,4

DNP). An affinity column is being used to purify the monoclonal antibody.

We plan to measure the enthalpy of the antigen-antibody reaction using

microcalorimetry and to measure the equilibrium binding using dialysis

techniques. Differential scanning calorimetry will also be used to

characterize both the bound and unbound antibody.

7. Plans for Next Year

Thermodynamic formation properties of the five and six membered

monosaccharides will be determined using available literature, estimation

methods and data from ours and others research. The study of the

thermodynamics of the reactions of glucose and fructose with ATP and the

isomerization of glucose 6-phosphate to fructose 6-phosphate will be

completed. The thermodynamics of the reactions of a monoclonal antibody

with its antigen will be completed. An examination will be made of the

thermodynamics of the most important processes currently used industrial

biotechnology. The available thermodynamic data will be given, best

available values will be recommended and, where appropiate, experiments

suggested. A thermodynamic investigation of the enzymatic conversion of

penicillin G to 6-aminopenicillanic acid and phenylacetic acid will be

initiated. Equilibrium measurements will be made using HPLC and, if

kinetics allow, microcalorimetric studies will also be pursued.

B. Differential Scanning Calorimetry

(F. P. Schwarz and W. H. Kirchhoff)

Differential scanning calorimetry, provides thermodynamics information

on biological systems which characterizes the interactions and

conformational changes of biological molecules in solution. Studies of

the effect of ligand concentration on the transition temperature and

enthalpy of protein, such as human serum albumin, yield informacion on

the binding energetics of the substrate to the enzyme. Comparison of the

transition enthalpies and temperatures of synthetic oligonucleotides

in solution yield information on the effect of the nucleotide sequence on

the conformational stability of DNA species in solution.

9
1 . Temperature and Enthalpy Standards for Differential Scanning

Calorimetry

(F. P. Schwarz)

Differential scanning calorimetry standards for temperature and

enthalpy are needed to validate comparisons of data from different

laboratories. A differential scanning calorimetric standard should

exhibit a well characterized transition in the temperature range from 0 to

100 °C , the normal operating temperature range for biological studies,

with an accuracy in the transition enthalpy of ± 0.10 meal and a temperature accuracy of ± 0.10 °C. It is also desirable to use a biological solution as a standard since many of the differential scanning

calorimeters contain fixed cells which are filled through small capillary

tubes. Ribonuclease A is a candidate. Ribonuclease A is an enzyme

consisting of 124 amino acid residues (G.M.W. = 13,700). In buffer

solutions, ribonuclease a exhibits an unfolding transition with a transition temperature and enthalpy depending on the pH of the solution.

It is readily available in relatively high purity and is highly stable.

Furthermore, its concentration can be readily determined by several simple

spectroscopic methods.

Solutions of ribonuclease A in a HCL-glycine buffer were prepared,

dialyzed, analyzed, and thermally scanned on a differential scanning

calorimeter to evaluate the suitability of ribonuclease A as an enthalpy

and temperature standard. The calorimetric results from solutions prepared from four different samples of ribonuclease A were determined with a computer-controlled, heat flow differential scanning calorimeter. The

solutions ranged in concentration from 0.7 to 1.7 mM and a glycine buffer

concentration of 0.1 and 0.2 M. A straight baseline was interpolated

under the transition peak to obtain the enthalpy of transition. The transition enthalpies exhibited a linear dependence on the transition temperature, ranging from 66.0 ± 0.4 kcal/mole at 37.4 ± 0;1 °C (pH = 1.9), to

110.0 ± 0.5 kcal/mole ac 64.0 ± 0.1 (pH = 4.2), with a standara deviation of 2.47 kcal/mole. The enthalpy determinations are in good agreement

with values reported in the literature. The results are independent of the source of the ribonuclease A and the concentration of the buffer. The solutions are stable when stored in a refrigerator and can be analyzed by

measuring the UV absorption at 278 nm at a pH of 7.0. An error analysis

revealed that the major source of error was in determining the temperature

limits in the integration of the enthalpy transition peak. It is anticipated that a computer algorithm based on the two state model, being developed by W.H. Kirchhoff, to fit the entire thermal scan, will further reduce

the standard deviation in the linear fit of the enthalpy to the temperature .

In summary, from the standpoint of ease of preparation, ease of

characterization of the transition properties of ribonuclease A, and

stability, ribonuclease A is an acceptable standard for the calibration of

differential scanning calorimeters. The value of a ribonuclease A

standard for measurement accuracy of the transition enthalpy and

transition temperature is expected to be improved by the algorithms being

developed

10
2. Studies of the Thermal Stability of Synthetic, Quasipalindromic

DNA Sequences in Solution.

(M. Miller, F.P. Schwarz, E. Appella (NIH) , and W. H, Kirchoff)

Oligonucleotides consisting of prepared palindromic sequences

have served as model systems for studying the effects of environmental

variable (e.g. pH, temperature, electrolytic strength, etc.) on the

stability of various forms of DNA - duplex (Z or B double-helix

structures), cruciforms and hairpin loops. The palindromic sequences, which

have the property of being self-complementary enabling the

oligonucleotides to form exactly matching double-helices or exactly

matching ends for stabilizing loop structures, have been extensively

studied by crystallography, differential scanning calorimetry,

UV spectroscopy and NMR. From these studies, the stabilities of all possible

nearest-neighbor configurations have been computed and from this limited

data base, the stability of any double-helix form of DNA may be estimated

from its base-pair sequence.

We have begun to study a series of quasipalindromic sequences in

order to determine the effects of mismatches on the stability and structure

of DNA. In addition, spectroscopic and calorimetric measurements on systems with small enthalpies of reaction provide very broad transition

envelopes which can further test mathematical models for the description

of phase transitions in small systems. This work complements structural

work being conducted in the Biomolecular Structure Group of the division.

The species studied, along with their duplex and hairpin forms are shown

below

.

1 3-mer 17 -mer 1 5-mer

CGCG AATT^CGCG

GCGC^TTAA GCGC

T A T

A A

GHC

C=G

GfC

CHG

CGCGCG AATT-^CGCGCG

GCGCGCf^ TTAA GCGCGC

T

A T

A A

G=C

CHG

GHC

CHG

GHC

CHG

CGCG AAATTT^CGCG

GCGC;^TTTAAA GCGC

T

A T

A T A A

GHC

CHG

GHC

CHG

One of the variables in the study of these species is the total

concentration of DNA strands. At high concentrations, the duplex form is

favored. At low concentrations, the hairpin form is favored. The high

concentration forms are most easily measured with a differential scanning

calorimeter, the low concentration forms with a uv spectrometer. Both

techniques were used and transitions between the species were analyzed.

The van’ t Hoff enthalpies of transition were most accurately determined

from the UV data. The 15-mer was found to form the most stable duplex

form at low temperature and was selected for crystallographic studies. The

thermodynamic data have been interpreted in terms of the relative

11
strengths of GrC vs A=T base pairs. Circular dichroism measurements

indicate the presence of the Z form of the duplex and observed transitions

have been tentatively ascribed to Z-B transitions.

3. The Effect of Ligand Concentration on the Thermal Stability of Human

Serum Albumin

(F.P. Schwarz and A. Shrake)

Serum albumin is the most abundant protein in blood plasma, and

information on its thermal stability can be used to improve commercial

preparations of blood plasma. A detailed differential scanning

calorimetry study has been completed on the dependence of the thermal

stabilization of human serum albumin on the concentration of alkanoate

anion ligands in solution. The increase in the thermal stabilization of serum albumin is monitored by the increase in its denaturation temperature

and in its denaturation enthalpy in the presence of increasing ligand

concentration. Two trends in the thermal stabilization were observed:

(1) The optimum denaturation temperature increased from 66.1 *^C in the

absense of ligand to 76.1 °C in the presence of formate and then to 79.0 °C

in the presence of acetate, propionate, and butanoate.

(2) The optimum denaturation temperature increased to 81.2 °C in the

presence of pentanoate and monotonically thereafter with increasing carbon

chain length to 88,8 °C for the decanoate anion. An increase in thermal

stability with chain length is anticipated since the binding constants of

the alkanoate ligand to the serum albumin increase with chain length. The

departure of propionate and butanoate from this behavior have been

explained by assuming two different types of binding sites for the ligand to

the serum albumin: (1) A large number of sterically hindered binding

sites which bind only small ligands (formate to butanoate) and (2) a small

number of large binding sites which bind all the ligands from formate to

decanoate

For FY 87, a number of studies are being planned which should serve as prototypes for assessing the applicability of DSC to the measurement of

protein-substrate binding energies. The studies currently under

consideration include: the thermal stability of monoclonal antibodies and

their complexes with antigens; the thermal stability of the avidine

and its unusually strong complex with biotin (vitamin H) , and the effects

of structural alterations on the thermal stabiliity of chymotrypsin and

trypsin and their respective proenzymes, chymotrypsinogen and

trypsinogen

4. Calculational Methods for the Characterization of Phase Transitions

in Biomolecules

(W. H. Kirchhoff)

Computer programs have been written for analyzing phase transitions in

biomolecules as measured by calorimetry or spectroscopy. The purpose of

the programs is to characterize the measurement process and to determine

the limits within which simple thermodynamic theories can duplilcate

temperature profile measurements. Since the same theories are applied to

both spectroscopic and calorimetric profiles, we may be able to separate

instrumental effects from effects due to the non-ideality of true phase

transition behavior.

12
The basis for the description of the spectroscopic and calorimetric

profiles is the explicit dependence of the concentration of species on temperature. Phase transitions can be considered to be chemical reactions

between initial and final states and can be written most generally as:

A <=> nB

and the concentration of species in states A and B is expressed in terms

of the equilibrium coefficient

K = [B]*^ and its temperature dependence d[lnK]/dT = “AH/RT^.

[A]

The enthalpy change, AH, is expressed as a power series about the standard

state temperature, T^:

AH = AHO + ACpO(T-TQ) + _

.

The expression for the differential scanning calorimetry heat capacity,

dQ/dT, is

dQ/ dT = -AH(dN^/dt) + N^Cp^ + NgCpp + baseline parameters

while the expression for the temperature dependence of the spectrum of a biomolecule undergoing a phase transition is given by:

^ baseline paramenters

were and Ig are the absorption coefficients or scattering intensities

for the two species (which themselves may be expressed as power series in

temperature). Simple algebra provides explicit expressions for dQ/dT and

for I as functions of temperature.

Computer programs have been written for fitting these expressions by

the methods of non-linear least squares to the experimental data. From

the spectroscopic data, Tq and AH° can be obtained, though the data are generally not sensitive enough to determine AC In the cases tested thus

far, which have included the main phase transition in lipid bilayers, DNA

fragments, and ribonuclease , the data have been fit to within experimental

error. As a corollary, additional information may be obtainable from

spectal measurements only through improved sensitivity, precision and

temperature control.

From the calorimetric data, T^, aH°, ACp°, and N, the number of

moles of material present in the cell, can be determined. This approach

differs from traditional approaches to the analysis of calorimetric data

in that the baseline is a varying function of composition, and hence

temperature. A so-called calorimetric enthalpy is not calculated.

Instead, the van' t Hoff enthalpy, AH°, and the number of moles, N, are deemed the fundamental quantities to be determined. Although the fit of

the model to experimental data seems excellent on casual inspection (the

observed and calculated profiles are indistinguishable in graphical

depictions) the difference between the calculated and observed profiles

shows distinct trends and the standard deviation of the fit is an order of

magnitude greater than the scatter in the data. This systematic error

may be due to diffusion and other dynamic effects which have not been

13
included in the analysis, the inadequacy of a simple power series in

describing the instrumental background or a breakdown in the purely two

state nature of the transition in ribonuclease A. Work in the coming year

will focus on distinguishing between instrumental effects and effects due

to the limitations of the purely thermodynamics model. The programs will

also be expanded to include values of n greater than 1 , the only case for

which the programs have thus far been tested.

The computer programs have been written in standard Fortran 77 for

personal computers compatible with the IBM AT and XT computers. In

developing the programs, some degree of portability had to be sacrificed

for ease of use. The lack of portability is related directly to the

graphical displays that accompany the analysis. At this time, no standard

protocols for graphical displays for Fortran-based programs exist. The

programs are currently being distributed on a limited basis to those

individuals who are willing to share their experience with the programs

and who can offer critical reviews of the thermodynamic models, the

statistics of the data analysis, the robustness of the algorithms, and

ease of use.

The function for the spectral profiles is known as the logistic

function and is commonly encountered in chemistry and other fields.

Consequently, the spectral fitting program has been written in a more

general manner for wider dissemination. It has been successfully used

to analyze sputter depth profiles through interfaces where a simple

diffusion model gives rise to the logistic function. The program has been

distributed to laboratories performing depth profile analyses and is

gaining in popularity.

14
3. BIOMOLECULAR STRUCTURE

A. Wlodawer, G. Gilliland, R. Harrison, M. Miller,

H. Savage, I. Weber

The Biomolecular Structure Group has developed an active program in

measurement and analysis of the structure of biological macromolecules. We

are developing new methods of X-ray and neutron structure determination

and are applying these and other, more conventional, methods to selected

structures of proteins and nucleic acids. Our general aim is to advance

the understanding of the structure-function relationship in macromolecules,

in particular by modifying the structure using genetic technology, by

binding of ligands and by studying families of closely related proteins

with different properties. We are also interested in the interactions of

macromolecules with solvent, and such studies can particularly benefit

from the availability of neutron diffraction data.

The physical facility available to us includes a well-equipped

general purpose laboratory for protefn purification, crystal growth and

mounting, including a walk-in cold room, as well as computer and graphics

areas. Instrumentation include a flat-cone neutron diffractometer located

on the NBS Reactor, a conventional X-ray generator with two Buerger

precession cameras (useful for preliminary data collection, but not for

intensity measurements), and a gas-flow crystal temperature controller

with a range of -80 °C to +60 °C. In the reporting period, we had no facilities for quantitative x-ray measurements, owing to the slow delivery

cycle of a Nicolet area detector. For these reasons our capability to

collect data was limited to the time donated to us by Cenex Corporation,

in collaborative efforts with Dr. Gary Gilliland, who subsequently joined

our group in August 1986. Our computing facility includes an IBM4381

shared with the Quantum Chemistry Group of the Molecular Spectroscopy

Division, a dedicated Evans and Sutherland Graphics facility which was upgraded this year from PS330 (vector graphics) to PS3^0 (vector and

raster screens). This modification enables us to create both dynamic

line drawings as well as static space-filling pictures. We have

implemented programs for hard copy output of the images generated using

various graphics programs. A recent upgrade to our computational facility

includes a MicroVAX II equipped with a large disk and a tape drive, which

will be dedicated to processing area detector data.

A number of problems initiated previously were continued in the last

year and several new ones were initiated. Those individual projects on which significant progress was achieved are summarized below.

A. Structural Studies of Mutations in Catabolite Gene Activator Protein

(I.T. Weber)

Catabolite gene activator protein (CAP) regulates transcription in E. coli in response to the level of cyclic adenine monophosphate (cAMP)

which is an allosteric activator of CAP. CAP recognizes and binds to

specific sequences of DNA at several operons, causing the stimulation or repression of transcription of cAMP-dependent genes. The crystal

structure of a dimmer of CAP with bound cAMP has been determined at 2.5A

resolution and refined to an R factor of 0.207.

15
Several laboratories are investigating mutations in the crp gene

that produces CAP. Three CAP mutants, 91, 220 and 222, that function in

the absence of cAMP have been subjected to crystallization trials in order

to study the structural changes associated with these mutations in amino

acid sequence. Both CAP 91 and 222 form crystals with cAMP. CAP 91

also crystallizes in the presence of adenosine, an alternate activator for

this mutant.

X~ray intensity data have been obtained for the crystals of CAP91

with CAMP which are isomorphous with the crystals of wild type CAP. These

data have been refined to 2. HA resolution and an R factor of 0.186. The

CAP91 structures are very similar although the Ala to Thr mutation is

clearly visible. There also is a movement of Cys178. There are no significant differences around cAMP-binding sites. Smaller differences

have been located by a vector average of the differences in atomic

coordinates. These differences are located far from the site of mutation,

in the hinge region between the two domains In the CAP subunit and In an

-adjacent loop -between two 6 strands. These differences suggest that the

Ala IHH to Thr mutation In CAP91 produces structural changes that

propagate through the hinge region towards the DNA-binding site.

The CAP91 structure is being investigated in the absence of cAMP and

in the presence of the analog, adenosine. Other CAP mutants will be

studied.

B. Predicted Structure for Two Domains of the Regulatory Subunit of

cAMP“dependent Protein Kinase

(I.T. Weber)

The mammalian cAMP-dependent protein kinase is an important

regulator of many biochemical reactions. In the inactive state the

holoenzyme consists of a complex of two regulatory subunits and two catalytic subunits. This is activated by the binding of cAMP to the regulatory subunits which then dissociate from the catalytic subunit. The

active catalytic subunit phosphorylates other proteins. The regulatory

subunit (R) contains two domains that bind to cAMP and have amino acid

sequences that are homologous with the sequence of catabolite gene

activator protein (CAP) from the bacterium, E. coli .

The crystal structure of the cAMP-binding domain of CAP has been used

to model the cAMP-binding domains of the regulatory subunits. The amino

acid sequence for the R-subunits was fitted into the CAP structure using a computer graphics system. The predicted R structure was overall very

similar to CAP. The model structure was evaluated by comparison with

other experimental evidence including photolabeling with 8-azido cAMP,

the binding of cAMP analogs, and fluorescence quenching. This gave good

agreement and the predicted structure of the regulatory subunits can be

used as a model for site directed mutagenesis.

C. Structural Studies of Anti-tumor Amidohydrolases

(I.T. Weber, A. Wlodawer and R.W. Harrison)

Three homologous bacterial amidohydrolases with anti-tumor properties

have been crystallized: a glutaminase-asparaginase from Acinetobacter

glutaminasif icans (AGA), a glutaminase-asparaginase from Pseudomonas 7A

16
(PGA) and an asparaginase from Vibrio succlnogenes (VA) . These enzymes in

solution are tetramers with subunit molecular weights of ca. 3^|000

daltons. AGA crystallizes in space group 1222 with one subunit per

asymmetric unit. PGA crystallizes as a tetramer in space group P2^2i2-|

and VA crystallizes in the same space group with a dimer in the asymmetric

unit.

Native data are available to 2.9A resolution for AGA and MIR data on three derivatives (5.3 to 4.0A) permitted the direct phasing of 2617

reflections. Phase improvement and extension to 2.9A resolution for an additional M784 reflections was achieved by two complementary techniques

of density modification. These are the method of B.C. Wang which

flattens the solvent region and improves protein connectivity, and the

method devised by R.W. Harrison that maps the distribution of density

values onto a Gaussian distribution with the same mean and standard

deviation. By examining electron density maps produced by the two

methods it proved possible to trace a polypeptide chain, although the

connectivity is ambiguous in several places. Since the amino acid

sequence has not yet been determined, the type of amino acid was estimated from the shape of the electron density, and these coordinates

were refined to an R factor of 0.30. The AGA polypeptide chain folds into

two domains. The first amino terminal domain, contains a f ive-stranded B sheet

and four of helices. The second domain has four of helices and several

6 strands. This model for the AGA structure has been used to phase the PGA

data.

Intensity data have been obtained to 2.5A resolution for the PGA

crystals using a Nicolet-Xentronix area detector at Genex Corporation.

The starting point for phase determination has been rotation and

translation function techniques using the AGA map. This solultion was confirmed by using the AGA polyalanine coordinates. The rotation function

has also been solved for VA. A starting PGA model was produced by

rotation and translation of an AGA tetramer and this was refined to

improve the phases. The tetramer model phases are being used as a prior

in the maximum entropy technique that is under development by R.W.

Harrison and the new electron density map is being intepreted. An active

site inhibitor has been soaked into the PGA crystals in order to locate the

active site of the enzyme.

D. Comparison of Two High Resolution Structures of Bovine Pancreatic

Trypsin Inhibitor

(A. Wlodawer, with J. Deisenhofer and R. Huber (Max Planck Institute,

Munich)

)

While it has been known for a long time that the structure of a protein in a crystal is similar to that present in solution, the limits of

discrepancy have not been rigorously established. The availability of

two distinct crystal forms for bovine pancreatic trypsin inhibitor

(BPTI) made it a system of choice for such studies.

The structure of deuterated crystals of form II of BPTI has been

refined using X-ray and neutron diffraction data. These crystals belong to

space group P2^2i2, a=74.1A, b=23.^A, c=28.9A and the packing of the

molecules is related to form I structure previously solved in Munich by

rotation of about 45® around y. X-ray intensities were collected on form

17
II crystals by the Munich group using standard diffractometry , while

neutron data extending to 1.8A resolution were collected at NBS. Joint

restrained refinement using both types of data was performed by J. Walter

and A. Wlodawer, resulting in a final model characterized by R values of

0.200 (X-ray) and 0.197 (neutron).

The two available high resolution structures of bovine pancreatic

trypsin inhibitor, refined in two distinct crystal forms, have now been

compared. After superposition, the molecules show an overall

root-mean-squares deviation of 0.^0 A for the atoms in the main chain,

while the deviations for the side chain atoms are 1.53 A. The latter

number decreases to 0.61 A when those side chains which adopted drastically different conformations are excluded from comparison. The discrepancy between atomic temperature factors in the two models was 6.7 A^,

while their general trends are highly correlated. About half of the

solvent molecules occupy similar positions in the two models, while the

others are different. As expected, solvents with the lowest temperature

factors are most likely to be common in the two crystal forms. While the

two models are clearly similar, the differences are significantly larger

than the errors inherent in the structure determination. This study

established the limits of discrepancy of atomic coordinates of proteins

which can be expected to result from differences in crystal packing.

E. High Resolution Refinement of Ribonuclease A

(A. Wlodawer, with G. Gilliland and B. Finzel (Genex Corporation),

A. Svensson and L. SJolin (Chalmers Polytechnic)).

The structure of ribonuclease A was reinvestigated using a new set of

X-ray diffraction data extending to 1.26 A, the limits of detectable

diffraction. The X-ray diffraction data were obtained frcxn two

phosphate-free crystals which were isomorphous with previously reported

monoclinic crystals containing phosphate, or perhaps sulfate. The data were collected using an area detector, the Xentronics-Nicolet image

proportional counter at Genex, and included 129,69^ observations of 25,732

unique reflections out of the total of 31.730 possible at 1.26" A. The data

scaled with a weighted least squares R-factor on intensity for

symmetry-related observations of 0.05, with 23,398 of the measured unique

reflections having significant intensity (F>2a(F)).

One of the first significant observations with the new data was the

detection of a large number of side chains with multiple conformations.

The structure was highly refined (R = 0.15) and was modeled with 13 residues having discrete multiple conformations of side chains. These residues are widely distributed over the protein surface, but only one of

them, Lys 6l , is involved in crystal interactions. The discrete

conformers have no unusual torsion angles and their interactions with the

solvent and with the atoms of the protein are similar to those residues

modeled with a single conformation. For three of the residues, Val 43,

Asp 83 , and Arg 85, two correlated conformations are found. The observed

plasticity in the protein surface will be of significance in analyzing

structure-function relationships and in performing protein engineering.

Other new observations resulting from this refinement, in particular

the details of the structure of ordered solvent, are still being analyzed.

18
F. StrucLure of the Solvent in Crystalline BPTI

(R. Harrison and A. Wloaawer)

Neutron data for bovine pancreatic trypsin inhibitor (BPTI) have been

collected for crystals soaked in both deuterated and hydrogenous solvents.

Deuterated data extending to 1.8 a resolution have been available for some

time, while hydrogenous data were collected recently. This data set was virtually complete to l.bA resolution, with 3^16 reflections showing

observed intensity.

Since deuterium and hydrogen have greatly different scattering lengths

it should be possible to use the difference between the scattering from

deuterated and hydrogenous crystals to determine the positions and

occupancies of exchangeable and solvent hydrogens. With X-ray diffraction

data, differences in the scattering due to a change in the crystal such as

the addition of a substrate can be used directly via a difference Fourier

synthesis to show the location and orientation of the changes in the

molecule or the complex. Because the differences are much larger with

deuterium-hydrogen exchange, such a simple treatment is not correct when

applied to neutron diffraction data. The problem with a simple treatment

is the choice of the phase of each term usee in the difference Fourier

synthesis. With small differences in the scattering there are only small

differences in the phase of the reflection. However, the phases of the

deuterated data and the hydroge.nous data determined by independently

refined models are quite different, and there is no a priori reason to

choose one or the other.

We have attempted to resolve this problem by constructing an enhanced

model of the scattering from the protein. The scattering is treated as coming from two non-overlapping regions. Scattering from the part of the

molecule that should not be altered by solvent exchange is required to be

the same in both the hydrogenous and deuterated models, and scattering

from everywhere else is independently refined for each model. Requiring

that the structure in the non-exchanged regions of the map be the same for

two different sets of data results in an improved model for the protein.

The solvent regions are required to be featureless when far (>^ a) away

from the protein. In addition a correction to the F(OOO) term of the

Fourier series is refined. These procedures should result in a significantly enhanced model for the solvent near the protein surface.

The structure of this local solvent is critical to the staoility and

function of proteins. The structure of solvent in BPTI is now analyzea in

tnese terms.

19
G. CrysLallization of Synthetic Fragments of DNA

(M. Miller, A. Wlodawer. and E. Appella (NIH))

We have been crystallizing a series of DNA oligonucleotides predicted

to form structures deviating from the classical double-helix. A 1 3“mer

d(CGCGAATTACGCG) derived from the self-complementary dodecaraer

d(CGCGAATTCGCG) by inserting an extra adenosine in the 9th position from

the 5'~end was synthesized as a model of a frame-shift mutation. This

sequence was expected to form an improper duplex with the unpaired adenine

residue either looped out or intercalated into the double helix. The

crystals that were grown were disorderd (or unstable). Our solution

studies (done in collaboration with F. Scnwarz and W. Kirchhoff of the

Biothermodynamic* s Group, see separate report) showed that the duplex

undergoes a transition to a single stranded hairpin loop in the temperature

range 0 - 6 °C. Subsequently we found that a 15-mer d(CGCGAAATTTACGCG) forms

a much more stable duplex. The inserted nucleotides are now separated by an AT sequence two base pairs longer. Crystals of this material have

been grown by the vapor diffusion technique at 4 °C. The space group is

1222 with a-36.9 A, b=53.8 A, and c-102.7 A. We are modifying the

conditions of crystal growth with the aim of preparing a sufficient

number of them for data collection. We have been also continuing our efforts to find a DNA oligomer which would crystallize in the form of a single stranded hairpin loop, but so far with little success.

H. Application of Repulsive Regularities Found in Water Structures.

(H. Savage)

Water structures in crystal hydrate systems have been studied in

order to categorize the repulsive interactions between different classes

of atoms (Nature 322 , 717,(1986)). These interactions are divided into

four groups (RR1 - RRA).

RR1 : 0...0 repulsion of the H-bonds (H-bonds may bend, if necessary, to

within a certain limit).

RR2: 0...0 repulsion between non-bonded water oxygens (minimum contacts

of 3 .I- 3 . 6 A depending on orientations).

RR3 : H2...01 repulsion between H2 and 01 of the configuration

01 -HI . . .02-H2 (minimum contacts of 3 .OA).

RR4 : H...H repulsions (minimum contacts of 2.1a).

(where HI, H2 , etc, refer to atoms belonging to two distinct water

molecules

)

20
These repulsive restraints explain several of the basic features

found in water structures. For example, they can be used to describe the

different structures found in the ice phase diagram. The

pressure-temperature phase space can be divided into 4 separate regions

(Fig 3-1) with respect to which of the repulsive restraints RR2 and RR3 are

fully strained:

Region 1 : H2. . ,01 remote contacts

,

Region 2: 0.. , .0 non-bonded contact

H2, . .01 remote contacts

Region 3: H2. ,.01 remote contacts.

Region 4; 0.

.

. .0 non-bonded contacts

H2. ..01 remote contacts

for a single lattice of H-bonds

for two interdigitating lattices of

H-bonds

In region 1 the RR3 contacts are fully strained, but the non-bonded

RR2 0...0 contacts are not (all >3.5A). Thus, a reduction in volume can oniy take place with respect to reducing the RR2 contacts. In region 2

both the RR2 and RR3 contacts are at their limit and further contraction

at higher pressures has to take place by the formation of interpenetrating

lattices of H-bonds (self-clathrates) . Compression of the 'double'

lattice follows along similar lines to that of the single H-bond lattice

case; firstly the RR3 contacts are fully strained (region 3), and then

both the RR2 ana RR3 contacts are at their minimuiji limits ^region 4).

In regions 1 and 3 the non-bonded RR2 interactions are not fully

strained and it is possible that some disorder of the water oxygens may be

present. This has been found in some recent ultra-high resolution neutron

diffraction experiments carried out at the Institute Laue-Langevin on ices

Ih (Kuhs and Lehmann, 1986) and VI (Kuhs and Finney, 1986). In ice Ih the

position of the oxygen was found to be disordered by up to 0.04 a, while in

Ice VI variations of up -0.1 5A are present.

I. Plans for Next Year

We are planning to commission the X-ray diffraction instrumentation

within the next few months. The system will consist of a Nicolet area detector mounted on a Huber dif f ractometer , with controlling electronics

locally adaptea by T. Buckley. When fully operational, this facility will

obviate the neea for the use of X-ray data collection facilities.

21
Temperature

Figc 3.1« Division of the pressure-temperature ice phase diagram into

four regions with respect to the RR2 and RR3 repulsive limitations

22
Scientifically, we are planning a concerted effort directed to

improving the ability to grow protein crystals in a predictable and

reproducible manner. To that effect, we will implement a crystallization

data base, originally developed by G. Gilliland at NIH, which lists all

published conditions for growth of macromolecular crystals. We will

develop software, in cooperation with the Chemical Thermodynamics Data

Center's Group for manipulation and updating of this data base.

23
CHEMICAL THERMODYNAMIC MEASUREMENTS

E.S. Domalski, S.S. Bruce, K,L. Churney, T.J. Buckley, J. Colbert,

E. Diaz, D.A. Ditmars, D.R. Kirklin, A.E. Ledford

A. Large Sample Combustion Calorimetry

(EeS. Domalski, J.C. Colbert, K,L. Churney, J.E. Diaz, A.E. Ledford,

S.S. Bruce, and T.J. Buckley)

This research is being performed in support of the Resource Conservation and Recovery Act and is funded by the U.S. Department of Energy.

The purpose of this work is to provide measurement methods, standards, and

baseline data for establishing calorific (heating) values and optimal

combustion conditions for the control of pollutants for municipal

solid waste (MSW) from various sources. Current emphasis is directed

toward monitoring the fate of chlorine from input through MSW combustion.

The presence of trace amounts of chlorinated organic compounds (i.e.,

dioxins) in the effluent and fly ash has hindered the construction and

operation of MSW incinerators used for the generation of steam and

electric power.

During FY 198M, samples of MSW were obtained from Brooklyn, NY, and

Baltimore County, MD to generate data on the chlorine content of MSW.

Quantitative information of this type is meager and is needed to evaluate

the methods that have been proposed for reducing the emission of

chlorinated dioxins and furans from incinerators. The main methods

proposed are: (1) removal of the responsible components of the waste, (2)

proper incinerator design, and (3) efficient operation of the incinerator.

The results of the sampling study, which were evaluated in 1985, showed

that all combustible components of MSW contained chlorine. Our study has

shown that removal of plastics from MSW is not sufficient to reduce the

chlorinated organic species formed during the combustion of MSW to

negligible levels.

During FY 1985, studies were conducted dealing with laboratory and

field data for the calorific value of MSW. The calorific value of the MSW

that is needed in a performance or acceptance test is the heat liberated in

the actual incineration process, however, the combustion of the organic

fraction of MSW is incomplete in this process. The calorific value

determined in laboratory tests is for conditions of complete combustion.

Currently, no data are available for validating methods either for the

measurement of incomplete combustion or the making appropriate

calculations to correct for incomplete combustion. To obtain such data,

the heat liberated for varying degrees of complete combustion was determined by burning microcrystalline cellulose and synthetic MSW in

O

2 /N2 mixtures containing 100, 50, 35, and 21 mole % O 2 in the O

2 in the

2,5 kg capacity flow calorimeter. The synthetic MSW is microcrystalline

cellulose which contains 20 mass $ silica as the noncombustible component.

The particle size of the silica and combustion conditions were such that the

amount of char formed in the combustion of the synthetic MSW in air was about 5$ of the mass of the ash, the approximate value for the amount of

char formed in MSW incinerators. Gaseous hydrocarbons and CO were monitored as a measure of gaseous products of incomplete combustion. The

combustion results are being examined to establish the methods for the

determination of calorific corrrections for incomplete combustion.

24
Also during FY 1985, studies were carried out to develop procedures

needed for the determination of the threshold conditions for the formation

and for destruction of organic chlorine compounds during MSW combustion.

The purpose of this study is to determine if we can reproducibly form

and/or destroy these compounds and, if so, whether the combustion

conditions in a large, laboratory-size combustor can be sufficiently

well-characterized to allow application of the results to design or operation of real-world MSW incinerators.

An EPA modified method 5 (MM5) gas and particulate sample train for

sampling the product gas and trapping, both particulates and volatile

organic chlorine compounds was constructed and installed as part of the

combustion flow calorimeter. Procedures were developed by S. Chesler and

R. Parris of the NBS Organic Analytical Research Division for separating

the organic chlorine compounds trapped in the MM5 train into chemical

classes of increasing clarity. The organic chlorine compounds were formed

in the combustion of synthetic MSW doped with 1.5 mass % polyvinyl

chloride (PVC) in 35 mass % O2/65 mass ? N2

. A qualitative analysis using

gas chromatography with an electron capture detector was carried out on

the separated organic chlorine product formed in the combustion of PVC

doped synthetic MSW. Dioxin or furans were not found but could have been

present below the detection of the instrumentation (several ppb), but

substantial quantities chlorinated benzenes, chlorophenols, and

chlorinated biphenyls (PCB’s) were detected.

In FY 1986, significant accomplishments were made in the following areas

1. Gram-size Test Samples to Characterize 2.5 kg Increments

An experimental test was conducted to verify the method

used to calculate the heat exchange between the 2.5 kg capacity flow

calorimeter and its environment. The test showed that the overall heat

exchange corrections to the experimental data were negligible, less than

0 . 1 J, despite significant departures from conventional gram-size

combustion calorimeter operating conditions. The results were used to

complete an evaluation of the bounds of systematic errors in the calorific

values determined in the FY 198^1 study involving gram-size test samples

prepared from kilogram-size parent increments. The results of the error analysis are reported in a manuscript describing the 2.5 kg flow

calorimeter and appears in the September 1986 issue of the NBS Journal of

Research

.

A summary of the results of the study concerning gram-size test

samples from kilogram-size increments was prepared and published in the

proceedings of the Twelfth National Waste Processing Conference sponsored

by the American Society of Mechanical Engineers (ASME) held in Denver, CO,

June 1986.

2. Chlorine Content of MSW

The results of the chlorine content of MSW study completed

in FY 1985 are in press for a 1986 issue of Chemosphere devoted to papers

presented at the 5th International Symposium on Chlorinated Dioxins and

25
Related Compounds held at the University of Bayreuth, West Germany,

September, 1985 and also appear in the Proceedings of the Twelth National

Waste Processing Conference sponsored by the American Society of Mechanical Engineers (ASME).

Four samples of MSW from Baltimore County, MD and Brooklyn, NY which

were analyzed in the 1985 chlorine content study were sent to R. Wingender

of Argonne National Laboratory for determination of the presence and

amounts of chlorinated dioxins, furans, and related compounds (e. g. PCB's

and chlorophenols) . Input composition data of this type are not clearly

established for MSW and are essential to establish how much dioxins or furans are formed during the incineration process.

3. Development of Corrections for Incomplete Combustion

The determinations of the calorific value and moisture content

of the cellulose burned in the study to develop methods for correction for

incomplete combustion were carried out. The determinations provide

necessary auxiliary data to convert laboratory results so that they have a closer correspondence to real-world incinerator conditions. The

combustion results obtained in the study for development of corrections

for incomplete combustion were summarized and appear in a second manuscript

published in Chemosphere (see following section).

Threshold Condition for Forraation/Destruction of Organic

Chlorine Compounds

The results of the FY 1985 combustion of synthetic MSW

doped with PVC appear in a second manuscript in press for Chemnosphere

,

devoted to papers presented in the 5th International Symposium on chlorinated Dioxins and Related Compounds.

5. Modifications to Apparatus and Procedures

A number of hardware and software changes were made as a result of the shift in emphasis of the experiments from calorimetry to

controlled combustion studies and chlorine monitoring. The changes were

as follows:

o To better simulate combustion conditions in real-world

incinerators, the combustor of the 2.5 kg capacity flow

calorimeter was modified so that the CO produced in the

combustion of synthetic MSW in air could be reduced to less

than 1000 ppm. (In the FY 1985 study to develop corrections

for incomplete combustion, the CO was in the 10,000-15,000 ppm

range.) This was accomplished in a sequence of experiments in

which various sources of heat loss from the combustion zone

(i.e. region near the burning sample) were successively

reduced, the most critical of which amounted to providing

insulation between the combustor and combustor enclosure in

the region below the reaction zone baffle. The option of

burning synthetic MSW in dispersed rather than in pellet form

26
was not explored in order to have a capability of studying the

formation or destruction of dioxins under various conditions

in the absence of fly ash.

o To minimize the time necessary to break down, reassemble, and

leak check the gas supply and sampling lines in a calorimetric experiments, the combustor was permanently

mounted on a frame outside the 2.5 kg capacity flow

calorimeter. Auxiliary cooling sources were built for the

outside of the combustor enclosure, for the heat exchange coil

for the product gas, and for the collector for the water

liberated in the combustion reaction to replace the cooling

originally provided by the calorimeter water.

o Two oxygen detectors have been installed to improve

the characterization of inlet and exit gas streams to the

combustor. Backup CO and CO2 detectors (NDIR) were installed in

the product gas analysis train to provide redundancy and loss

of data due to detector malfunction.

o To improve the collection of trace chlorinated organic

species, the MM5 train was redesigned and is being rebuilt in

cooperation with R. Wingender of Argonne National Laboratory,

who will carry out the dioxin analysis in subsequent

experiments. Changes are oriented towards improving the

efficiency of recovery of organic chlorine compounds and

reduction of possible contamination of the XAD-2 resin (used

to trap gaseous organic chlorine compounds) prior to analysis

by gas chromatography and mass spectrometry.

o To upgrade monitoring of the detectors for O

2 , CO and Co2

t a new

thirty channel scanner was installed. Since each combustion

experiment now tends to be quite different in terms of the

need for and time sequence for monitoring the various

detectors, the original software for data acquisition for the

fixed routine of a calorimetric experiment has become

obsolete and has had to be replaced. We were fortunate to

have a guest computer scientist from the Twente University of

Technology, Netherlands, to help us in redesigning the data

acquisition software. As a result of Mr. Rukkers three and a half month stay with us, we have a well designed data

acquisition system which can be modified rapidly to fit the

varying demands of any particular laboratory experiment.

Other software for data analysis and plotting was developed

by two summer students (S. Sung, R. Metz).

In the initial phase of the combustion experiments of

this study, we are currently carrying out a set of chlorine

mass balance experiments. The aim of these experiments is to

determine the degree to which suitable clean up procedures

will ensure that organic chlorine compounds detected in the

combustion products of a given run are formed from chlorine

containing compounds burned in the same rather than in

previous runs.

27
During FY 1987 we plan to complete the remaining auxiliary measurementa

and analysis of the study for development of corrections for incomplete

combustion. The initial phase of the study of threshold conditions for

the formation/ destruction of chlorinated organics will be completed with

an attempt to determine the combined recovery efficiency of the combustor

plus the MM5 sampling train for chlorinated organic compounds. In the

second phase of the study, we plan to evaluate the use of calcium oxide

binder in densified pellets of processed MSW as a possible method for

reducing dioxin emissions from combustion of refuse. In the third phase of

the study, we plan to resume our study of the combustion of synthetic MSW

doped with inorganic as well as organic chlorine compounds.

Because the combustor of the 2.5 kg flow calorimeter cannot be

economically altered to provide all the combustion conditions that must be

studied in the threshold study, a new laboratory- si ze , two stage

incinerator was purchased in FY 1986. It is our plan to instrument this

unit and conduct trial experiments toward the latter part of FY 1987.

B. Calorimetric Update on SRM Coals 2682, 2683, 2684 and 2685

(J.C. Colbert)

The annual calorimetric update was performed on SRM Coals 2682, 2683,

2684 and 2685 to determine if there has been any change in the calorific

value of these coals due to sample degradation as a result of aging or normal oxidation. Sixteen unopened bottles of coals were received from

OSRM, four of each of the latter SRM’s. One measurement was made for

residual moisture and one for calorific value. The original certified

value for sulfur was used in making the calculations since this

constituent remains constant with time. All of the measurements were made

in random order with one duplicate measurement for SRM 2684. The sampling

procedure and run protocol was designed by R.C. Paule, NML Statistician.

Good agreement (<50 Btu/lb) was obtained between calorific values

obtained for SRM 2683, 2684, and 2685 and their 1985 certified values,

however, the average calorific value for SRM 2682 was 300 BTU/lb higher

than the average result for 1985.

As a further check on the results, an additional set of four unopened

coals were measured with only one sample giving a high calorific value.

These eight coal samples were sent to an outside testing laboratory by

the OSRM. The results of our lab and the outside lab agree to within 7

Btu/lb. The final statistical evaluation of the data led the OSRM to

remove the calorific value certification from SRM 2682. This is

due to a larger variability in the sample than anticipated, resulting in a larger variability in the calorific value than was predicted. It appears

that the bottled material maybe degrading at an uneven rate, the cause of

which is unknown at this time. Another parameter which should be examined

is particle size variability in SRM 2682, within and between bottles,

since particle size variability can influence the dispersion of results.

28
C. Bomb Calorimetric Measurements for Biotechnology

(J'.C. Colbert and E.S. Domalski)

The enthalpy of combustion of the crystalline monsaccharides D-ribose

and 2-deoxy-D-ribose (2-deoxy-D-erythro-pentose) have been determined by

combustion bomb calorimetry. The standard molar enthalpies of combustion

(AjjH) and formation (AfH) at 298. 15 K for crystalline D-ribose are:

-23 ^ 9.47 ± 0.95 kJ/mol and -10^7.23 ± 1.66 kJ/mol, respectively.

Similarly, for 2-deoxy-D-ribose, A^H = -2527.39 ± 0.98 kJ/mol and AfH = -869.31 ± 1.68 kJ/ mol. Proton NMR and C-13 NMR studies were conducted by

B. Coxon of the Center for Analytical Chemistry, to determine the anomeric

composition of the crystalline sugars* The crystalline D-ribose sample

consisted of 6M.4 mass % beta-pyranose, 35.^ mass % alpha-pyranose , and

0.2 mass $ beta-furanose anomers. The sample of 2-deoxy-D-ribose was made

up of 98.8 mass $ beta-pyranose, 0.5 mass % alpha-pyranose, and 0.7 mass %

beta-furanose anomers.

Combustion bomb calorimetric studies are in progress on crystalline

hexaglycine. Elemental analyses on this compound for carbon, hydrogen,

and nitrogen from two independent testing laboratories indicates that it

is the hemihydrate. An examination of the literature combined with some Dreliminary calculations on diglycine, triglycine, and tetraglycine shows

that the energy of the peptide bond in these compounds is constant. If one extends this energy constancy to hexaglycine, then the energy or enthalpy of hydration can be estimated as a result of conducting the

combustion calorimetric measurements. This value for the enthalpy of

hydration should provide some useful insight into the magnitude of

hydration forces between an oligopeptide and water under conditions of

initial bonding interaction.

Previous bomb calorimetric measurements in this laboratory on crystalline adenine, guanine, purine adenosine, guanosine dihydrate,

D-ribose, and 2-deoxy-D-ribose provide the basis for establishing several

energetic cycles for the formation of nucleosides as well as indicating

research paths in which to pursue combustion bomb calorimetric

measurements on key compounds. Three key compounds which are immediate

candidates are: deoxyadenosine, deoxyguanosine, and nebularine.

Energetic differences between ribose/deoxyribose , adenine/adenosine,

guanine/ guanosine, and purine/ nebularine moieties in nucleoside formation

could be established more precisely than are presently available and could

be regarded as standard reference value points for thermodynamic

assessments involving reaction processes of nucleosides.

D. Estimation Methods and Combustion Calorimetry of Organic Phosphorus

Compounds

(D.R. Kirklin and E.S. Domalski)

Precise enthalpies of formation are not available for important

industrial and biochemical compounds that contain phosphorus.

Experimental determination of these properties for some of the compounds

is not feasible because of their toxicity or limited availability. The

objective of this research is to develop correlation and estimation

schemes which are needed to predict enthalpies of formation at 298 K for

29
ccxnpounds that have no reported experimental values. Also, combustion

calorimetric determination of enthalpies of combustion will be conducted

on key organic phosphorus compounds.

Precise and accurate enthalpies of formation are necessary to develop

an adequate correlation and estimation scheme. However, there is a lack

of precise and accurate thermodynamics literature data on organic

phosphorus compounds. The existing thermodynamic data for organic

phosphorus compounds, which are based upon bomb calorimetric data, are often inaccurate due to several problems associated with the combustion

calorimetry of organic phosphorus compounds. Until the present time,

there is only one set of data in the literature which has adequately

addressed all of these problans. These data were obtained by Harrop and

Head (J. Chem. Thermodynam. 9, 1067 (1977).) on crystalline

triphenylphosphine oxide.

There are four major problems associated with the combustion

calorimetry of organic phosphorus compounds. The first problem is the

selection of an unreactive crucible material. Platinum crucibles, which

work well with most organic compounds, are unsuitable because platinum

reacts with organic phosphorus compounds at high temperatures. The second

problem is that organic phosphorus combustion samples usually do not burn

completely in a bomb combustion experiment. Phosphorus compounds are used

commercially as flame retardants for various fabrics because of their

resistance to burning. When phosphorus compounds burn in oxygen they

produce oxides of phosphorus which dissolve in the water in the bomb to

form various kinds of phosphoric acids. These phosphoric acids have

appreciable energies of dilution and are produced as various

concentrations in different parts of the bomb. Therefore, the attainment

of a homogeneous solution of uniform concentration of these phosphoric

acids constitutes the third problem area. The fourth problem is that the

bomb solution must be analyzed to determine, qualitatively and

quantitatively, the speciation of phosphorus acids formed as rapidly after

the calorimetric measurement as possible because of slow oxidation of all

phosphoric acids present to H^POij.

The solution to the above mentioned problems are straightforward, but

most laboratories are not equipped to handle them. Gold crucibles are found to be unreactive with organic phosphorus compounds but have a relatively low melting point. A sufficiently massive gold crucible

performs well in most experiments. The problem of incomplete combustion

can be overcome by determining the amount of carbon dioxide produced or by

measuring the amount of carbon residue formed. The problem of obtaining a homogeneous solution of the phosphoric acids can only be solved by using a rotating bomb calorimeter. Most laboratories use static bomb calorimeters

and therefore cannot obtain a homogeneous bomb at the end of the reaction

period. The qualitative and quantitative analysis of bomb solutions can

be only done by various forms of chromatography. Harrop and Head used

paper chromatography, however, this method is very slow and not very

quantitative. Ion chromatography seems to be ideally suited to solve this

problem because it is quantitative and offers reasonable precision.

The NBS bomb calorimetry laboratory has a rotating bomb calorimeter

that utilizes sample sizes on the order of 100-200 milligrams. The

laboratory has equipment for measuring the amount of carbon dioxide

30
produced during each combustion experiment. A DIONEX 2000i Ion

Chromatograph was borrowed from the DIONEX Corporation to check the

feasibility of analyzing the bomb solution composition for the various

forms of phosphoric acids.

A set of measurements on triphenylphosphine oxide was made in the

NBS rotating bomb calorimeter. Negligible amounts of carbon residue were

produced. The carbon dioxide analyses verified these results. A DIONEX

2000i Ion Chromatograph was utilized to analyze the homogeneous bomb

solution for the various oxyacids of phosphorus. Orthophosphoric acid,

H^POn, pyrophosphoric acid, HnP20 y, and tri polyphosphor ic acid, HcP^O-iQf

were observed to be produced in the following percentages, respectively:

76 . 3 , 20.0, and 3- 7. The analysis means that 59.9 % of the total

phosphorus was quantitatively converted to orthophosphoric acid while

3 i.il % and 8.7 % of the total phosphorus was converted to pyrophosphoric

acid and tripolyphosphoric acid, respectively. These values were used to

determine the amount of energy that would be needed to hydrolyze the

condensed phosphoric acids to orthophosphoric acid.

A correction of -11.08 J/g for the hydrolysis of condensed phosphates

to orthophosphate was added to our experimental energy of combustion, -35,

778.15 ± 5.06 J/g, for triphenylphosphine oxide to calculate the correct

energy of combustion, -35,789.2 ± 5.06 J/g. This value agrees very well

with the previous reported value of -35,789.6 ± 6.0 J/g by Harrop and

Head. (J. Chem. Thermodynam. 9, 1067 (1977)). These authors have reported

the only precise combustion data for an organic phosphorus compound which

was based on a comprehensive analysis of the products of combustion, which

included the quantitative determination of condensed phosphoric acids

present in the bomb solution from a rotating bomb calorimeter. Bedford

and Mortimer (J. Chem. Soc. 1622 (i960)) reported an energy of combustion

of -35,943 ± 45 J/g based upon measurement using a static bomb

calorimeter

.

Experimental measurements were also made on triphenylphosphine. The

methods and procedures established during the triphenyl phospohine oxide

were utilized. The sample was vacuum dried for 12 h and found to contain

0.0077 $ moisture. The sample was investigated with no further

purification. The mean of seven measurements yielded a value of

“39,200.73 ± 3.85 J/g for the internal energy of combustion without a correction for the hydrolysis of condensed phosphates to orthophosphate.

Assuming that the condensed phosphates were produced in the same proportions as for the triphenylphosphine oxide would require an additional correction of -11.08 J/g. This would make the actual value

determined to be -39,211.81 J/g. However, the actual correction for the

hydrolsis of condensed phosphates must be determined on a set of

combustions of triphenyl phosphine and will be performed during fiscal

year 1987 when the combustion calorimetry laboratory receives a DIONEX Ion

Chromatograph. The internal energy of combustion reported by Bedford and

Mortimer is -39,245.8 ± 36.7 J/g based upon measurements using a static

bomb calorimeter.

31
Future plans Include bomb calorimetric measurements on other key

organic phosphorus compounds. These measurements will provide the data

necessary to determine estimation parameters for other organic phosphorus

compounds. Proposed compounds are triphenyl phosphate, tri-n-octyl

phosphine oxide and tricyanophosphine.

E, Drop Calorimetry of Non-Reacting Systems Below 2800 K

(D.A. Ditmars)

This activity is a continuation of a calorimetric research program

whose goals are:

o to obtain accurate thermodynamics data on non reacting refractory

materials in either the solid or liquid state up to 2800 K.

o to measure the specific heat at temperatures above 273 K of

well-characterized materials of the highest attainable purity for which

existing Cp data are insufficient or in conflict and which are: (a)

critical to energy and space related technology, or (b) especially suited

as a model on which to test refined lattice-dynamic calculations of

thermodynamic properties.

o to produce and support high- temperature calorimetric standard

reference materials (SMR*s) for heat capacity and for differential

thermal analysis (DTA) calorimetric measurements.

The number of facilities, nationally, which can sustain programs of

high- temperature calorimetric research is seriously diminishing at a time

of increasing needs for just the data produced through this type of

investigation. There is a constant demand for thermodynamic data on new materials capable of functioning acceptably in the harsh environments

associated with space propulsion systems or upon re-entry, new energy

technologies and defense-generated needs for materials to enable space

systems to withstand overt aggression. Also, the existing thermodynamic

data on some elements is often not accurate enough to allow a meaningful

test of theories which have recently been formulated to calculate

thermodynamic functions directly.

The Chemical Thermodynamics Division has available two operative

precision drop calorimeters for the ranges 273“1200 K (isothermal,

phase-change calorimeter) and 1200-2800 K (adiabatic receiving

calorimeter). These are being used in research intended to provide

calorimetric measurements at the highest accuracy on materials related

to the high temperature applications mentioned above. Every effort is made

to coordinate this research with that of another NBS facility

(very-high-temperature pulse calorimeter) in order to provide the capacity

for continuous coverage of high- temperature thermodynamics studies up to

5000 K or above on especially important systems. We have in addition an operative high- temperature discrete-heating adiabatic calorimeter (300-800

K) and we maintain in reserve a low- temperature (4-300 K) adiabatic

calorimeter for possible future research needs.

32
In order that NBS thermal data and that of other hlgh-temperature

investigations can be fairly intercompared and assessed for accuracy, we

maintain a continuing effort to update or extend the range of coverage of

high-temperature standard reference materials. In recognition of the

growing need for accurate DTA temperature and enthalpy standards, we attempt to identify systems whose thermal properties can be measured by

both conventional calorimetric and DTA techniques.

We have concentrated our experimental and data-analysis activity in

FY 1986 among the alkaline earths Ca, Sr, and Ba and have continued our work on pure Cu. Of the alkaline earths, calcium is of particular

economic and biological importance, yet the literature thermodynamic

functions for calcium are certain to be seriously in error due to sample

impurity effects. The situation of the thermodynamic functions for

strontium is similarly unclear for no original published heat-capacity

data exists for this element above room temperature. This is unfortunate,

as knowledge of the thermodynamic properties of strontium compounds

figures prominently in assessing the course and effects of potential

nuclear power accidents.

In the conduct of thermodynamic research on these alkaline earth

metals, one must confront the effects of low, but virtually irreducible,

oxide and hydride impurity levels which nevertheless exert a substantial

influence on the phase relationships among the allotropes of Ca and Sr

and on Ba. Thus, a large fraction on ones total effort must be devoted

obtaining pure samples, maintaining their integrity, and obtaining

credible analysis for the oxygen and hydrogen present.

Our prior (FY 8^) heat-capacity data on calcium, measured partly at

NBS (T>300 K) and partly at the U.S. Geological Survey in Reston, VA (in

the cryogenic range) employed two calcium samples of differing oxygen and

hydrogen impurities. Of these data, only those in the high- temperature

fee region (715>T>300 K) were obtained using the sample of lower purity.

Comparison at NBS with enthalpy data obtained in the fee region for the

high-purity sample led to the conclusion that the earlier NBS

high- temperature data were subject to serious and uncorrectable systematic

error arising from the method of encapsulation. Therefore, in FY 86 we repeated the entire fee series of measurements on the higher-purity

sample. In addition, a number of enthalpy measurements were made at

closely and carefully-spaced temperatures throughout the fcc-bcc

transition region. This new fee data for calcium was analyzed in FY 86

and shown to merge, uncorrected, with the cryogenic data mentioned above.

The enthalpy data for calcium in the fcc-bcc transition region indicated

not a sharply temperature-resolved transition, but one occurring gradually

over a 5 or 6-degree interval. This, we have interpreted using a model in

which a trace contaminant (in this case CaH2) enters into ideal solution

with each of two allotropes of calcium. The results (Fig ^.1) indicate a lower

temperature for the fcc-bcc transition temperature (710 K) than current

values proposed in the literature (716 to 720 K)

.

Analysis of the strontium sample we had obtained from Prof. Westrum of the

University of Michigan measured in FY 86 showed an unacceptably high level

of hydrogen contamination. Therefore, we obtained in FY 86 a new,

33
specially-prepared , diff usion-distilled strontium sample from the

Metallurgy Department of Iowa State University. At the same time, we

obtained a similar sample of barium.

Considerable effort was expended in FY 86 on the encapsulation of these

materials and preparation of them for purification of hydrogen as well as for oxygen and hydrogen analyses. To bring this about, we developed a cooperative arrangement with the Metallurgy Division of the Naval Research

Laboratory (Wash. D.C.) for the use of their electron-beam materials-processing facility.

In FY 87 we plan to extend the heat capacity measurements on calcium

through the melting point into the liquid range. Also, purification and

analysis of the strontium and barium samples will be carried out and

measurement of their heat capacity in the solid range begun. Heat

capacity measurements on the purified barium sample in the cryogenic range

will concurrently be performed. In FY 86 we collaborated with a guest

worker from Brock University (C. Flint, Ontario) to complete measurements

on the heat capacity of highly-pure, polycrystalline copper (NBS Special

Research Material 5 : a low- temperature heat capacity standard) up to 1173

K. We plan to extend these measurements in FY 87 to the melting point and

to begin the analysis of our data and comparison to the extensive

literature data available on copper. These copper data will have potential value in extension of the temperature range of the copper heat-capacity standard and in establishing more accurate heat capacity data against

vrtiich to test new theoretical model in the calculation from first principles of the thermodynamic properties of fee metals.

T/K H/J mol

(a) (b)

Fig. 4 . 1(a); Idealized Ca-CaH2 phase diagram including 2-phase region

near peritectoid. Overall CaH2 concentration (Co)= 0.24 mol % ? (b): Schematic measured enthalpy function for Ca containing

0.24 mol % CaH 2 in solution. 714 K, T 2= 720 K, = 710 K.

34
5 . CHEMICAL THERMODYNAMIC DATA ACTIVITIES

M.W. Chase, D.M. Bickham, D. Garvin, C.R. Jackson, T.L. Jobe, Jr.

W.L. King, D.B. Neumann, V.B. Parker, D. Smith-Magowan, R.H. Wood,

(Consultant), D.D Wagman (Guest Worker), E.D. Hearing, R.H. Nuttall,

R.H. Schumm, N. Young, and S.D. Wasik (Contractors)

The goal of this work is to provide reliable values of thermochemical

and thermophysical properties of chemicals, both inorganic and organic. The

values are intended to be useful throughout science and industry. Because of

the widely differing needs of users, emphasis is placed in this work on generic information and methods of wide applicability. Two data centers carry

on this function: the Chemical Thermodynamics Data Center (CTDC) and the

Electrolyte Data Center (ELDC). Both are partly supported by the NBS Office

of Standard Reference Data (OSRD).

The data group now consists of five thermochemists, a computer systems

manager, two computer programmers, a chemical information specialist, a clerk, a consultant and a guest worker. In addition, four thermochemists do

special tasks under contract.

The work of the two data centers is inter-linked. Together they cover the

evaluation of thermochemical properties of chemical reactions, thermal functions of chemical species and thermophysical properties of solutions. These

activities are being extended by extramural collaborations: participation in

the CODATA Thermodynamic Tables project to build an international set of

recommended values, and, cooperative work with the University of Delaware on methods for correlating thermophysical properties of solutions.

A major expansion of the data centers occured during the year. The JANAF

Thermochemical Tables project was moved to NBS from the Dow Chemical

Co., Midland, MI. Dr. M.W. Chase, leader of the JANAF project, became a member of the data center staff, and, at the end of the year, head of the

Chemical Thermodynamics Data Centers Group.

The data centers are supported by a vigorous computer group which

manages the mini- and microcomputer facility used by five CCP data

activities

.

The outputs from the centers are published in the Journal of Physical and

Chemical Reference Data, the Journal of Research of NBS, CODATA Special

Publications, Handbooks of DIPPR, and proceedings of various meetings. The

annual index to the thermochemical literature on inorganic compounds that is

prepared at NBS is published in the Bulletin of Chemical Thermodynamics.

Most of our prime activities are described in the following paragraphs.

Topics in progress which will not be discussed further are:

o Installation of the computer program GAMPHI (calulates activity

coefficients) on a microcomputer

35
o Final selection and documentation of the CODATA key values for

chemical thermodynamics

o Preparation of recommendations for the solubility of eleven types of

organic compounds in water

o Converted network calculation programs (CATCH) to be operational on

the NOS CYBER (from the NBS UNIVAC); these programs are necessary for

the evaluation of the calcium and key values results for CODATA and the

rubidium network

A. Chemical Thermodynamics Data

1 . Thermochemistry of Compounds of Iron

(V.B. Parker)

The evaluation of the thermochemical properties of iron compounds

is being undertaken as part of a larger project, sponsored by CODATA, that

will include thermal functions and the analysis of several binary systems.

The thermochemical analysis is well underway. A reaction catalog (listing of

pertinent measurements, each expressed as a chemical reaction, together with

the values of the properties measured) has been assembled. It contains the

evaluated thermochemical data on the reactions of the "key” iron compounds.

A "key" compound is a species whose thermochemical properties are of

strategic importance because many other compounds are dependent upon its

thermochemical properties. The properties of this compound may, in turn, be

dependent upon those of other compounds (from various reaction paths). This

group of compounds and its interconnections comprises the "key network".

The thermochemistry of iron compounds is complex. An example of this

complexity is shown in Figure 5=1, which indicates the enthalpy relationships

among the key compounds. A similar diagram, not shown, indicates the Gibbsenergy relationships and measured entropies. Considering the importance of

iron and its compounds, the disarray of the data for the basic thermochemical

relationships is disturbing. Calculations of the same property via different

paths in the network yield discordant values. This is demonstrated in the

following brief analysis of the thermochemical properties of Fe'*’^(aq) and

Fe'*'3(aq) in their standard states at 298.15 K. The cited reactions are from

the network shown in Figure 5.1, the values are from individual studies or combinations of them. The enthalpy data are given first for the two ions and

then the Gibbs energy data. The tentative selected values made to date

conclude the presentation. The state designation "ao" means standard state.

All thermochemical values are in kJ/mol.

Enthalpy of Formation; For the determination of the enthalpy of formation of

Fe"^^(ao) the measurements on the following reactions are used.

(1) Fe(cr) + 1 .5H202(ao) + 3H'*'(ao) = Fe'*’3(ao) + 3H20(1)

(2) FeCl

2 (cr) = Fe'^^(ao) + 3Cl“(ao)

36
(3) Fe(cr) + 1.5Cl2(g) - FeCl3 (cr)

(H) Fe(cr) + 3HCl(in

+ H20(1)

12.73 H

2 O) + 0,5H202(1) - FeCl3(cr) + H2(g)

Values obtained are:

From Reaction AfH°(Fe'*’3,aq) Aj*H°(FeCl3,cr

)

(1) r46.6±0.8

(2) and (3) “53«8±0,9

(2) and (M) “57.0±1 ,0

(3) “396.02±0.1i|

(4) “399.24±0.35

The agreement of the results in each column is not as good as anticipated,

baaed on the claimed reliability of the individual studies.

Similarly a more extensive set of measurements may be used for the determination

of the enthalpy of formation of Fe‘*'^(ao). A similar conclusion is obtained.

The resulting values show too much scatter; much larger than would have been

expected based on interpretation of the Individual studies.

In a third independent path, the difference between the enthalpies of

formation of ferric and ferrous ion can be determined from;

(5) Fe'"2(ao) + 0.5H202(ao) + H*"(ao) « Fe'^^Cao) + H20(l)

(6) Fe'^^Cao) + H^(ao) - Fe'"3(ao) + 0.5H2(g).

Again, from a collection of six results, the scatter in this enthalpy of

formation difference is too great, casting suspicion on the results,

Gibbs energies of formations: The Gibbs energies of each of these species can

be determined (independently) from cell measurements (7), equilibria and

solubilities (8-10).

(7) Fe(cr) + 2H'*'(ao) - Fe^^(ao) + H2(g)

(8) Fe'^^(ao) + 2Tl(cr) - Fe(cr) + 2Tl‘^(ao)

(9) (1/3) Fe304 (cr) + 2H'*’(ao) + (1/3) H

2 (g) = Fe‘"^(ao)

+ (4/3) H20(1)

(10) FeSO^ ;7H20(cr ) - Fe^^(ao) + S04 “^(ao) + 7H20(1)

The Gibb's energy of the ferrous ion AfG®(Fe'^^,ao) is determined to be:

37
from (7) from reaction shown

“80.U±0.20 “78.7±1o5 (8)

“90e11±0.80 “90.0±5«0 (9)

”78„8±0.5 “90,6±1 .2 (10)

“84 . 9

^0.20

These numbers should exhibit much greater agreement. On the basis of the EMF

data alone, a value AfG°(Fe'^2 ,ao) of“80.1i|± 0.20 would be selected, using a study in which great care was taken to avoid electrode contamination by

H

2 (g)(from its preparation) and 02 (g). The more negative values from (9) and

(10), however, cast suspicion on this choice.

The Gibbs energy of formation of ferric ion, “11.M±1.5 kJ/mol can be

obtained from:

(11) FeOOH(cr, alpha) + H20(l) - + 3 0H“(ao)

where AfG°(FeOOH, cr) is dependent upon AfH°(Fe20j4 ,cr ) and

S®(FeOOH, cr, alpha).

Independently, the half cell

(12) Fe"^2(aQ) + H'^(ao) = Fe‘*’3(ao) + 0.5H2(g)

for which agreement among the various investigations is excellent,

yields A( AfG°(Fe'"3(ao)-Af.G°(Fe'"2,ao)) = 74.27±0.20.

Selected values. Tentative selections have been made, based on the data given

above;

Fe'*'^(ao)

Fe‘^3 ( ao )-Fe'*’^ ( ao

)

so that:

Fe'^^(ao)

FeCl2(cr

)

FeCl2(cr

FeS04:7H20(cr)

AfH°

“91 o5±1 .0

“119.0±2.0

“3^2. 8±1 .1

“396,0±2.0

“3013. 7±0.

A(AfH°) A(AfG°)

M2.5±1.5 7^.27±0.20

It is hoped that further analysis of the data, and the inclusion of more

data, based on current measurements, will help establish the selections above

and clarify the situation, particularly that for AfG°(Fe'*'2,ao) . The

following experimental data would be useful.

Activity coefficients for aqueous FeSO^^ solutions. Those used now for

^solGO(FeS0i| ;7H20,cr ) are estimated from NiSOn, but it is not known how good

this analogy is.

38
IRON

KEY

NETWORK -

ENTHALPY

H c n X3 3O n

L. 3

U,

Fig.

5.1.

Iron

Key

Network —

Enthalpy.

Measured

processes

are

shown

by

ai

connecting

the

substances.

(The

numbers

on

the

arrows

refer

toa

larger

reaction

catalog

than

that

discussed

here,

and

are

not

the

same

as

those

the

text).
o The AfG°(Fe‘^^,ao) value, now -80.14 ± 0,20 from EMF data

should be verified.

o AsoiHsoiH(FeCl 3 ,cr ) is needed as a function of concentration in water

and aqueous HCl. The present data are not of high enough quality to

permit confident extrapolation to the standard state,

o AfH°(FeCl 2 ,cr), AfH°(FeCl3 ,cr )

,

and ApH° for FeCl 2 (cr) + 0.5 Cl 2 (g) » FeCl^Ccr) should be redetermined. The FeCl 2 /FeCl couple is important

outside the iron system as auxiliary data in redox reactions. The ”NBS

Tables” and others use - -57,5, but there are conflicts in data

in the uranium halide thermochemical network which might be a result

of using this value.

2. JANAF Thermochemical Tables

(M.W. Chase)

This project was transferred in February 1986 from The Dow Chemical

Company, Midland, MI to the Center for Chemical Physics at the National

Bureau of Standards. Since that time, most of the effort has been directed at

the establishment of JANAF resources within the Chemical Thermodynamics Data

Centers. This includes the calculational programs, the literature and data

files, and the backup information for the existing tabulations. In parallel

with this, the third Edition of the JANAF Thermochemical Tables has been

completed, at Dow Chemical, and sent to the American Institute of Physics for

publication later this year in Journal of Physical Chemical Reference Data.

In our data evaluation activities reviews and thermochemical tables are being prepared for three classes of species: the alkaline earth metals, their

monohydroxides and their dihydroxides. For the 3rd Edition of the JANAF

Thermochemical Tables, the calcium thermal functions were estimated to be

intermediate between those for magnesium and strontium; the strontium thermal

functions being based on unpublished enthalpy data of Stephens and Roth.

However, there now is additional Information available from the recent heat

capacity study of calcium by Robie (USGS) and the enthalpy studies of calcium

and strontium by Ditmars. The low temperature study by Robie is in

qualitative agreement with the recent JANAF analysis. However, the

experimental results yield a considerably different Cp curve in the region

below ~20 K, raising the entropy of calcium at 298.15 K by - 1 .5 J/(mol K)

above our recommendations. When the analysis of new information is completed,

the thermodynamic functions of the metals will be much more firmly based. We

will then be in a better position to judge the reliability of the existing

enthalpy data for barium.

The alkaline earth monohydroxides have been studied experimentally

during the last few years. A thorough spectroscopic study has been carried

out for the magnesium, calcium, strontium, and barium species by Harris et

al. and Bernath et al. These studies have yielded structures and two of the

three vibrational frequencies v-,

, and V2

- In all cases, vo, the 0-H stretch is

assumed to be -3650 cm-1 in comparison with the alkali metal hydroxides. Now

the thermal functions, in particular the entropy, are well-established, in

comparison with the previously available entirely-estimated values. This

40
results in the entropy at 298.15 K being shifted by 2.5 J/(mol K). However,

for the case of beryllium, we still must rely on theoretical calculations for

the structure and the vibrational frequencies.

Our review of the alkaline earth dihydroxide species is nearing

completion. The full analysis of these species is limited by the lack of low

temperature heat capacity data for Sr( 0H )2 and Ba( 0H )2 and high temperature

enthalpy data for Be(0H)2. The low temperature data for Be(0H)2 has been

measured in USSR, is available through VINITI (Russian Depository of

Technical Data), and will enhance the quality of the beryllium dihydroxide

thermal functions. The gas phase dihydroxide species are estimated based on comparisons with the gaseous difluorides, dichlorides and the monohydroxides.

With more reliable data avalilable on these latter species, the resulting

gaseous dihydroxide thermal functions (still estimated) should be much

improved

.

In addition, information has been collected for the analysis of the

alkaline earth oxides, sulfides, sulfates, carbonates, and the halides. For

each of these classes of species, annotated bibliographies exist and are being updated continuously. Data summaries are in preparation for these

classes of species.

3. Thermochemical Properties of Compounds of Rubidium

(V.B. Parker, W.H. Evans, R.L. Nuttall)

The thermochemistry of rubidium compounds has been summarized in a paper accepted for J. Phys. Chem. Reference Data. This paper presents a catalog of the 420 measurements on 250 substances used in the preparation of

the rubidium table In the ”NBS Tables of Chemical Thermochemical Properties'*.

It represents a comprehensive survey of thermochemical measurements on rubidium compounds. Included are enthalpies of reaction, Gibbs energies of

reaction, based on equilibria and cell potentials, and entropies. For each

process a comparison is made between the observed value and that calculated

from the "NBS Tables". A feature novel to thermodynamic tables is that

estimated reliabilities are given for the recommended values for each

measured process.

4. Thermodynamic Properties of Compounds of Calcium

(D. Garvin, V.B. Parker)

The first volume of a new series of tables of evaluated

thermodynamic properties of chemicals is being published this year. It is the

"CODATA Thermodynamic Tables. Selections for Some Compounds of Calcium and

Related Mixtures. (A Prototype Set of Tables.)", D. Garvin, V.B. Parker and

H.J. White, Jr., editors. This is the report of the CODATA Task Group on Chemical Thermodynamic Tables and covers six years of work by an international team of data evaluators. NBS has taken the lead, providing

evaluated thermochemical data, a definitive analysis of the CaCl2-H20 system, some thermal functions, extensive "catalogs of data", technical editing and

preparation of the final book. Its contents are summarized below.

Recommended values are presented for chemical thermodynamic properties of

selected compounds of calcium and their mixtures. These have been prepared in

accord with and as a test of a plan developed by the CO DATA Task Group on

41
CODATA THERMODYNAMIC TABLES

Substance Molar mass AfH‘<0 K) AfH" AfG' H‘-H*(0) $

g.mol"^ “• J.(mol .K)’'* ••

M8(cr> 24.3050 0 0 0 4.998 32.671 24.869

COOATA Kay Value C84C00I. ±0.030 ±0.100 ±0.100

Mg(l) 24.3050 4.790 14.044 9.788 a 1.633 34.309

Extrapolated froa high ±1.0(M ±1.200 ±1.000 ±2.000 ±3.000

tanparatura.

Mg(g) 24.3050 145.901 147,10 112.521 6.197 148.649 20.786

COOATA Kay Value C84C00]. ±0.800 ±0.80 ±0,800 ±0.002 ±0.005 ±0.001 MgO(er) 40.3044 •597.422 -601.60 •569.311 5.160 26.950 37.237

COOATA Kay Value (84caoi. ±0.300 ±0.30 ±0.30 ±0.020 ±0.150 ±0.200

MgF2(cr) 62.3018 • 1120.297 -1124.2 •1071.051 9.920 57.200 61.587

COOATA Kay Value C84C003. ±1.200 ±1,2 ±1.300 ±0.060 ±0.500 ±0.2

Ca(cr) 40.0800 0 0 0 5.736 41.588 25,929 COOATA Key Value C84C001. ±0.040 ±0.400 ±0.300

Alpha

Ca(er2) 40.0800 1.056 0.614 0.792 a 43.070 25.951

Beta, extrapolated from ±0.300 ±0.800 ±0.300 ±0.700 ±1 .200 high temperature.

Ca(l) 40.0800 7.788 6.619 13.524 a 45.510 35.000

Extrapolated from high ±1.000 ±1.200 ±1.000 ±2.000 ±3.000

temperature.

Ca(g) 40.0800 177.339 177.80 144.020 6.197 154.887 20.786 COOATA Key Value C84C00]1 . ±0.800 ±0.80 ±0.810 ±0.002 ±0.004 ±0.001

Ca*(g) 40.0795 767.152 773.81 732.057 6.197 160.650 20.786

±0.830 ±0.83 ±0.84 ±0.002 ±0.002 ±0.001

Ca'^^lg) 40.0789 1913.645 1926.50 1880.218 6.197 154.887 20.786

±0.920 ±0.92 ±0.930 ±0.002 ±0.005 ±0.001

Ca'*’2(ao) 40.0789 •543.0 -552.807 •56.2 •281.38 COOATA Key Value C84C00] . ±1.0 ±1.100 ±1.0 ±5.0

Ca^Cg) 80.1600 341.982 341.7 289.819 11.190 257.185 36.577

±1.800 ±1.7 ±1.800 ±0.100 ±1.500 ±0.500

CaO(cr) 56.0794 •631.594 •634.92 •603.297 6.750 38.100 42.049 COOATA Key Value [84COO] • ±0.900 ±0.90 ±0.920 ±0.060 ±0.40 ±0.400

CaO(g) 56.0794 24.623 23.5 0.974 8.953 219.718 32.455 ±8.000 ±8.0 ±8.000 ±0.001 ±0.020 ±0.010

Fig. 5.2. Selected values for AfH°. AfCo, K), S°, Cp at 298.15 K an AfH°(0 K) at 0.1 MPa. First page of a 5 page table of thermochemical data in

the CODATA Thermodynamic Tables.

42
Chemical Thermodynamic Tables. All values in the present table are mutually

consistent and are consistent with the CODATA Key Values for Thermodynamics.

The values are recommended for general use.

The evaluated data are for common compounds of calcium (element, oxide,

hydroxide, peroxide, fluoride, chloride, sulfate, nitrate and carbonate,

their hydrates and their ions in aqueous solution) and for three systems:

Ca-Mg, CaCl2“KCl and CaCl2~H20.

Forty one tables of thermal functions (heat capacity, entropy, enthalpy and

Gibbs energy functions) are given for those compounds of magnesium, calcium

and potassium for which the properties have been evaluated in this

work. Twenty four tables of thermal functions are given for auxiliary substances. Each table spans the temperature range 0 to MOOO K, to the extent

that data are available. Formation properties at 298.15 K (enthalpy and Gibbs

energy of formation) are given for 68 compounds of calcium, magnesium and

potassium plus the relevant values of 5^ auxiliary substances. A sample f>age

from the' formation property table is given in Figure 5.2.

For each of three binary systems recommendations are given for mixing

properties (enthalpies and Gibbs energies), partial molar or excess properties of the components (activities, enthalpies, heat capacities) and

phase transformation' data. All selections of data are accompanied by

uncertainties, and are documented. Detailed lists of the measurements used in

the evaluations are given for the thermochemical, alloy and aqueous solution

sections.

The preparation of this compendium involved work at five geographically

separated institutions, assembly of machine readable data bases, transfer of

data by magnetic tape and interactively, and extensive development of com- puter programs for both thermodynamic calculations and document preparation

and printing.

5. Needs for Thermochemical Data

(D. Garvin, V.B. Parker)

In the course of work on the CODATA Key Values for Thermodynamics

and the CODATA tables on calcium compounds, deficiencies in the presently

available thermodynamic data have become apparent. Very brief summaries of

these are given here. Publication of this material is planned, in order to

alert the thermodynamic and spectroscopic communities to these needs.

(a) K

2 (g): Dissociation Energy. The 1930's spectroscopic data

(used in a Birge-Sponer extrapolation), the vapor pressure data and recent

theoretical calculations do not agree (range kJ). Current spectroscopic

techniques are adequate for the solution of this problem.

(b) Ca(cr): Thermal Properties. Ditmars (NBS) and Robie (U.S.G.S)

have measured the heat capacity of Ca up through the alpha-beta transition.

On the basis of preliminary results, their work leads to a value for 3(298.15

K) that is 1.5 J/(mol,K) greater than the CODATA Key Value, to different heat

capacities for the alpha and beta forms, a lower 710 K versus 716 K,

and a revised A^pHA^pH. (Only the liquid remains to be done). These data, if

accepted, will change selections for all species whose properties depend on

high temperature data, such as Ca(g), a CODATA Key Substance, CaH 2 (cr), and

43
possibly Ca(0H)2(cr) and CaCO^Ccr). Gibbs energies of calcium compounds will

also change. However, these changes, <0.5 kJ/mol of Ca, usually are less than

the uncertainties in the values themselves.

(c) CaCl2.nH20(cr ) , n= 1,2, 4, 6: Heat Capacity. These hydrates are

the stable forms of the salt in equilibrium with aqueous solutions, “50 to

+175 °C. For none of them are there low temperature Cp data from which

entropies can be calculated. Instead, the entropies are calculated from

enthalpy and Gibbs energy of solution data, and the resulting values of S do

not show the smooth variation that might be expected. Recent measurements by

Meisingset and' Gronvold treat the hexa-, tetra- and di-hydrates above 288 K

and can be combined with low temperature data to provide the thermal

functions needed for a modern optimization of the CaCl2“H20 system. Such data

will also be useful in the development of estimation methods.

(d) CaF2 (cr): Solubility and Thermal Properties. Existing

measurements give pKgp values varying from 11.6 to 8 at 298.15 K. The likely

value is 10.6, although the most recent extensive study gives 11.6.

Solubility should be studied between 298 and 500 K (to allow for geochemical

applications), from both under- and over-saturation as a function of ionic

strength, acid concentration, particle size, time to reach equilibrium,

source and preparation of the samples. Choice of method will be important.

In addition this substance has a lambda- type transition in the heat

capacity at 1424 K. There are enthalpy measurements, but these are insufficient to define the transition. Heat capacity measurements are needed.

(e) Ca(0H)2(cr): Enthalpy of Formation. The "best” data lead to

Aj«H values that do not mesh well with those for CaCO^ and CaO. Nor do the

Gibbs energy data (solubility and high temperature decomposition). Enthalpy

of solution and solubility studies should be repeated.

(f) Ca'^^(aq,std. state): Entropy and Enthalpy of Formation. This

Key Substance has surprisingly poorly defined properties: S to ±1.0 J/mol K,

AfH to ±1.0 kJ/mol. Its properties are based on those of Ca(0H)2f CaSOn,

CaCO^ and Ca(N02)2 and their aqueous solutions. The spread in values from

system to system is larger than within each system. Any type of

experimentation that would improve the properties of Ca'^^(aq) would be

useful

(g)

CaO(cr) and MgO(cr): Enthalpy of Fusion. Both of these

substances melt above 3000 K. Measurements of have proved to be very

difficult, the melting point of CaO may still be in dispute. The enthalpies

of fusion are derived from phase boundary information: d(ln a^)/dT= Af^gH^/R.

Older values are 77 kJ/mol for MgO (from the Mg0-Zr02 system) and 52 kJ/mol

for CaO (Ca0-Zr02 system), in both cases assuming ideal solutions. A recent

optimization of the MgO-CaO system [Chand and Howald, 1982] selected values

of about 58 kJ/mol for both, allowing for non- ideality in the liquid and

solid phases. Unfortunately, phase boundaries in the CaO-MgO system are very

poorly delineated and are based in part on studies that lead to incorrect

melting points. A comparative study of other binary systems should be made.

44
(h) CaMg2

; Therrnochemical and Thermophysical Data. The analysis of

this system in the CODATA Thermodynamic tables showed that the data are in

very poor shape. Enthalpy data above 298 K show large scatter, a new study is

needed. This may indicate that the limited low temperature heat capacities

need to be remeasured. Enthalpies of fusion measurements disagree, and are

not consistent with mixing data and enthalpies of formation. Almost any

attack would help.

B. Electrolyte Data

1 . Electrolyte Data: The Calcium Chloride-Water System

(D. Smith-Magowan)

Evaluation of data on the physical and chemical properties of

aqueous electrolytes is done by the Electrolyte Data Center with two

fundamental objectives: (1) to provide reference data for use in scientific

and technical applications and (2) to present data and analyses which will

highlight challenges for future experimetal or theoretical investigations.

The results of a study of the CaCl2-H20 system provide an example of the

realization of these two goals.

A correlation of experimental data on the heat capacity of CaCl2

solutions as a function of temperature and composition has been combined with

separate NBS correlations of excess Gibbs energy and excess enthalpy as functions of composition at room temperature to create a "skeleton table” of

values for all three properties throughout the temperature range

273*15“373.15 K and composition range 0-11 molal. The heat capacity correlation

was made using a model-independent spline fit on the T-x surface. The other

two correlations used the Pitzer formulation (although this was not

essential). The apparent molar heat capacities are shown in Figure 5.3. The

maximum with respect to temperature in the apparent molar heat capacity is

found in other salts and is analogous to the trends observed for excess

volume. This behavior has not yet been interpreted in terms of the structure

of the solutions.

The resulting values for the excess properties C_®*, H®* and G®* are considered to be the most accurate representation of the experimental data

available and cover the broadest range of composition of any study presented

to date. The procedure includes the systematic treatment of data on aqueous

systems at elevated temperatures, where the pressure is greater than one atmosphere. The effect of pressure has routinely been neglected in most

previous treatments of the data for this system. Comparison with previous

correlations where the effect of pressure has been neglected reveals a tangible systematic error in those studies.

Heat capacity data are lacking or of low quality in several temperature-composition regions. Below 298.15 K, the evaluation is based on scattered, imprecise data at intermediate compositions. More accurate measurements at all concentrations are desirable, but measurements below 1 molal

and above 8 molal are imperative if the correlations are to be improved. This

is an important temperature region as the structure of water and of solutions

is changing rapidly with temperature. Data at high concentrations (7 molal

to saturation) are needed at all temperatures. Experimental values are not

available, even at 298.15 K and estimates had to be made in our work, based

45
m LO LO lO

C\l

LO

ro

(,_(>i ioLu)r)/'*'‘'3

II

t.3

X

II

o

(0S

J o

O

£

a

II

II

II

o

O

fO&

<0o

(0

0) £

c

0>

to£Xa

<e

« jid mo m 1 too

« I bO on ^ E~-

fej c\j

LO

I
on a small set of measurements at 323 and 3^8 K. The high concentration

region is important because, more often than not, the industrial applications

involve concentrated solutions.

Enthalpy of dilution data are available only at or near 298.15 K. There is

only one published study that covers any large range of concentrations at

other temperatures (273 and 323 K). Above 298 K there are no data that reach

the saturation line. Most useful would be a study at 373 K, from 0 molal to

saturation, and a study at 323 K from 0 to m, to validate the existing study.

For both Cp and data from 373 K to the critical line will be welcomed.

This study has also raised a significant problem for the theoretical

interpretation of thermodynamic properties of electrolytes concerning the

permittivity (dielectric constant) of H20(l). It was necessary to choose a consistent formulation for the Debye-Huckel limiting law slopes Ax

(activities), Aj^( enthalpies) and Aj (heat capacities). Later on Ay (volumes)

will be required. The limiting law slopes for all properties can be

calculated for any temperature or pressure provided that the density, the

permittivity and their derivatives with respect to temperature and pressure are

known. The Haar-Gallagher-Kell equation of state for water (NBS-NRC Steam

Tables) is nearly a universal standard for the PVT properties of water. There

are available, however, several formulations for the dielectric constant of

water all of which represent the experimental measurements equally well, at

least superficially. Our first selection was the dielectric constant

correlation of Uematsu and Franck, because of the wide range of temperature

and pressure at which it is applicable, the extensive data base considered,

and its status as a standard.

A reviewer of the work pointed out that the formulation of Bradley and

Pitzer should be used as it more accurately reproduced the measured

permittivity values and derivatives at temperatures below 298.15 K.

(Differences in the calculated D-H limiting law values are inconsequential

for the Gibbs energy or enthalpy, but are quite dramatic, 30%, for heat

capacity.) The reviewer’s comment appears to be correct, and, because of our concern for fitting the lower temperature data, we have adopted his

suggestion for the present.

An ensuing examination of the available experimental permittivity data,

however, indicated they are not accurate enough for our purposes especially

below 298.15 K. There are several detailed studies that show similar trends

with temperature, but the studies disagree in absolute value. Thus it is

difficult to establish the second derivative. The data are compared in Figure

5.4. The trend with temperature (below 298.15 K) in the Bradley-Pitzer

formulation is steeper than in the Uemetsu*-Franck treatment, and is closer to

the trends in the principal studies. It is clear, however, that this

important property of an important substance needs to be redetermined.

47
Permittivity

of

Water

deviations

from

79BRA/PIT

O

O

03

O

00

o

1^

o

CD

O O o

o

o

roO

(N

O

O

ild/vdaez - dX3

'd- m

00

•H

48

The

two

correlations

represented

by

solid

points

are

compared

to

the

79

BRA/PIT

correlation.

Four

experimental

data

sets

represented

by

open

points

are

compared

to

the

BRA/PIT

correlation.
2. Krebs Cycle Thermodynamics

(D. Smith-Magowan)

The thermochemical analysis of the reactions comprising the Krebs

cycle has continued during the year. The value of the network method for

obtaining thermochemical properties for metabolic substrates has been shown

in several aspects of the work thus far.

Inconsistencies in the results for several reactions suggested, after some

thought, that the value of the reduction potential for the Nicotinamide

Adenine Dinucleotide/Nicotinamide Adenine Dinucleotide (NAD/NADH) couple

( 0.311 ± 0.006 V from potentiometric Measurements), which is widely adopted

and was input to the network, must be in error. This is indeed the case as our subsequent investigation revealed. It was discovered that an error in

the formation data for the reduction of acetaldehyde to ethanol obtained from

the compilation by Stull, Westrum and Sinke leads to an error in the

interpretation of equilibrium measurements for alcohol dehydrogenases from

which this potential has been deduced. Recent equilibrium measurements for

the acealdehyde/ ethanol system have been used to obtain a more reliable value

for the NAD/NADH potential (O .3165 ± 0.001 V) that is more consistent with

the other reactions of the Krebs cycle.

For many of the substances involved in the Krebs cycle it is virtually

impossible to obtain an estimate of the Gibbs energy of formation in solution

by the more traditional approach of combining enthalpy of reaction and heat

capacity determinations (to get entropies) for the pure substance with

measurements of the solubilities (to get because the necessary data

are lacking. Lactic acid, for example undergoes polymerization in aqueous

solution, making it impossible to measure its solubility accurately. Using

the power of the network analysis, which includes reactions linking lactate

with pyruvate, oxaloacetate, and acetate, a value for Gibbs energy of

formation (-519.77 kJ/mol) has been obtained that is accurate to ±0.M

kJ/mol. Similar situations can be quoted for other substances.

The Krebs cycle is common to almost all aerobic respiration pathways, which

implies, at least in principle, that the network can be extended to encompass

metabolic substances of unlimited complexity. If this is indeed possible,

it could be the most reliable way to quantify and relate the subtle effects

of changes in structure, in solution, of the complex substances that

biotechnology seeks to exploit.

3 . Electrolyte Solution Properties Data Base

(D. Smith-Magowan)

A computer database of thermodynamic properties for electrolytes

is being developed for the Design Institute for Physical Property Research

(DIPPR). DIPPR is sponsored by AIChE and is a consortium of about 50 major

chemical companies that support various research projects depending upon

their individual interests. The database will consist of a collection of the

activity, enthalpy, heat capacity and volume properties for electrolyte

solutions supplemented by computational utilities to aid the engineering

application of these properties. These utilities will provide the ability to

calculate values of properties for simple binary solutions using several

different models for extrapolation, prediction, or comparison; the

49
calculation of properties for ternary or more complex mixtures; and methods

for integrating these properties to obtain consistent sets of properties for

a range of temperature, pressure and composition.

4. Temperature-Density-Composition Correlations of Excess Properties

(D. Smi th-Magowan

)

The correlation of thermodynamic properties of electroytes as a function of temperature, pressure and composition is underway using an algorithm that simultaneously treats temperature, density and composition as independent variables. The experimental data for calcium chloride are being

used as a test case so that comparison with the CODATA skeleton table can provide an indication of the quality of the performance of this algorithm.

The choice of density as an independent variable instead of pressure is made

because of the PVT behavior of water at elevated temperatures. As the

critical point is approached, the compressibility of water increases greatly

and the excess thermodynamic properties of binary electrolytes appear to show

corresponding trends. For example, the apparent molar heat capacity (at

constant pressure) of aqueous NaCl seems to diverge to a value of negative

infinity as the temperature of the critical point (6?4 K) of water is

approached. A polynomial in temperature to fit such behavior requires terms

of very high order. The heat capacity at constant density (or volume) on the

other hand, is not divergent and can be fitted with a less complicated

expression.

C. Thermodynamic Properties of Organic Compounds

(E.S. Domalski, E.D. Hearing, J.F. Liebman, D. Garvin)

1. Prediction of Properties

An estimation method developed by S.W. Benson and coworkers for

calculating thermodynamic properties for gas phase organic compounds from

structural group parameters has been extended to the liquid and solid phases

for hydrocarbons. The work is in the process of being reviewed for

publication in the Journal of Physical and Chemical Reference Data.

The group parameters for hydrocarbons in gas, liquid and solid phases at

298.15 K have been tested in 1267 comparisons with experimental data. For 527

comparisons with enthalpy of formation data, the average difference is ± 2.8

kJ/mol. The average differences for 396 comparisons for heat cap>acity and 344

comparisons for entropy in all three phases are ±2,6 and 3*1 J/(mol.K),

respectively. The publication will include examples of the method of

calculation, total symmetry numbers and methyl corrections for hydrocarbons

plus a bibliography on the development of estimation methods since 1932.

This estimation procedure is now being extended to C-H-0 compounds in the

gas, liquid and solid phases at 298.15 K, and it is planned to apply it to

C-H-N and C-H-N-0 compounds

2. Thermochemistry of Organic Compounds of Interest in

Biotechnology

A preliminary machine-readable data base has been compiled for

evaluated data on the chemical thermodynamic properties of a thousand organic

compounds at 298.15 K. Four general classes of compounds are covered, all of

50
interest to researchers in biotechnology, namely: (1) amino acids, peptides

and related compounds, (2) heterocyclic nitrogen compounds, (3) heterocyclic

oxygen compounds, and (^) heterocyclic sulfur compounds. The properties

covered are enthalpy of combustion, enthalpy of formation, heat capacity,

entropy, Gibbs energy of formation and the logarithm of the equilibrium

constant of the formation reaction. The data base is now being annotated.

Publications are planned for each section.

3. Enthalpies of Combustion of Components of Natural Gas.

Recommended values have been prepared and published for the

enthalpies of combustion of the C^ -Cg alkanes, C2 “ C3 alkenes, acetylene,

benzene and C3 - Cg cyclolkanes. In addition to the thermochemical data,

corrections are given for non-ideal behavior of the gases. This work has

been incorporated in a handbook on properties of natural gas for use in the

liquified natural gas industry (prepared for the International Group of

Importers of Liquified Natural Gas, GIIca^L) , included in the Gas Producer

Association standards, recommended to ASTM, discussed withan ISO Task Group,

and reported on at an industry conference on "Gas Quality". In the course of

this work it has been noted that thermochemical data for the hexanes are conflicting. Predicted enthalpies of combustion (and formation) of

2,2-dimethyl and 2,3“dimethyl alkanes tend to be outliers in estimation

schemes. That is true for the hexanes 2, 2-dimethyl butane and 2, 3~cli methyl

butane. Their enthalpies of combustion also are the least well defined of

those for the lower molecular weight hydrocarbons. Calorimetric,

isomerization equilibrium and correlation results spread by 2.5 kJ/mol.

Combustion calorimetry on these two hexanes (now known only from relative

measurements) could lead to a solution of the general problem of how to treat

such isomers.

D. Automating Data Center Procedures

(D.B. Neumann, D.M. Bickham)

Automation efforts in the Chemical Thermodynamics Data Centers are oriented toward providing for the following needs: (a) data analysis, (b)

on-line access to data and bibliography, (c) transfer of data to other media

or other data bases, (d) re-formatting data for publication, and (e)

graphical presentation of data.

This year, three generic solutions to data center problems have been developed. The problems are: search for and retrieval of chemical data,

bibliographic data management, and, printing and publication of results. The

solutions are applicable to the work of all the CCP Data Centers.

1. Search and retrieval systems.

A general keyed access search-retrieval system called SETKY-GETKY

has been written and implemented on the HP-1000. It is suitable for indexed

material containing either text or tabular material.

SETKY-GETKY provides rapid access to free formatted textual or tabular

material stored in large data files on the mini-computer. As a "keyed access"

system it permits the user to create editable files with the usual system

editor. Index commands, or "keys", are placed into the file by the user.

51
SETKY is then invoked. It reads the original file and creates a file of keys

that will be searched. The key file contains only the keys and the physical

disc positions of the text in the original file to which the keys refer.

In its on-line mode the user invokes GETKY with a key or an approximate

key. The GETKY program rapidly searches for the key in the key file. Using

the physical disc position retrieved from the key file, GETKY retrieves, by

direct access in the original file, the indexed item of text and displays it.

If the key cannot be found, Getky returns the 20 keys alphabetically nearest

to it and prompts the user to select one.

There are several aspects of the. system that has made it unique and highly

useful for Data Center work:

Text related to a key may be obtained from within programs, i.e. the

GETKY functions are callable from user programs. This has been used to

build retrieval systems for the JANAF Thermochemical Tables and the

CTDC abstract files.

The original text files can be used for text processing as well as for

on-line or programmatic retrieval. This has been accomplished by

choosing the syntax of the index commands in the original files to be

compatible with the TEXED system currently used for text formatting of

reports and papers. This feature has been used in building a system for

printing the CODATA Thermodynamic Tables.

The original file remains accessible, may be corrected or expanded by

its owner. (This is much easier than when a Data Base Management System

is used.)

The number of index items per entry is unlimited.

SETKY-GETKY is written in FORTRAN 77.

It is expected that these programs will be transferable to other systems

such as the NBS Cyber or micro-computers such as the IBM-PC/XT, or AT. It may

prove advantageous to use it as the search system for data distributed on

floppy discs.

A users guide for SETKY-GETKY is being published in the proceedings of

the 1986 International Users Group for Hewlett-Packard minicomputers. The

applications of the system to date are (1) in printing a large section of the

CODATA Task Group on Chemical Thermodynamic Tables, (2) a combined users manual and on-line help system for the HP-1000 was created, (3) a retrieval

system for the JANAF Tables, (4) the NBS Telephone Book on-line, and (5) a retrieval system for abstracts of thermochemical data.

The motivation to create the SETKY-GETKY system was to automate CTDC’s

large data base of literature extracts, some 50,000 in number. In FY86 a section of this data base was re-formatted for this application. Using this

section as a test we expect to remove remaining problems from the retrieval

system and put the entire data base on line in early FY1987. At that point

retrieval by substance formula, property, name, Wisswesser line notation,

and registry number will be possible.

52
2. Common Bibliographic System.

A bibliographic system for CTDC and the other Data Centers, DB-BIB, was placed on-line and is being tested. Initial test applications are with a small

Ion-Energetics bibliography and a bibliography of sputtering data (Surface

Chemistry Division). The goal of this effort is to load, as an on-line

searchable data base, all 60,000 -70,000 CTDC bibliographic citations. This

is necessary to permit the more efficient preparation and publication of

reaction catalogs such as that for rubidium thermochemistry, which is now in

press.

3. Printing and Text Formatting” Utilities. A program utility,

(called PTTL) , for printing using the OSRD laser printer was written by CTDC,

This system is now in use by the Atomic Spectra Data Center, the Kinetics

Data Center, and is used heavily by CTDC, Its function is to provide for suband super-scripts, Greek and math symbols, italics, bold, various line

spacing needs, as well as a general and consistent input technique for Data

Center staff. OSRD staff have made a number of improvements to this utility.

A utility for formatting reports containing text as well as tabular

material, called TEXDA, was implemented by CTDC on the OSRD and CTDC

mini-computers. It is an expansion of TE)CED distributed by the International

HP Users Group. A User's Guide covering both these utilities is in preparation

by OSRD.

M. CTDC Abstracts Data Base.

Twenty six hundred current articles on thermodynamics were abstracted during the ten months Nov 1985 through Aug 1986. The process for

doing this has been refined to make use of the Chemical Abstracts Data Base.

Articles of interest are selected by inspection of CA or of high-yield

journals. This is done by a contractor and by CTDC staff. The abstracts of

the articles are retrieved from CA and then a decision is made by CTDC staff

about the usefulness of each article and how it is to be abstracted. Copies

of the articles to be retained are obtained, if possible, and microfilmed.

Each article is indexed for its thermodynamic data content (in terms of

substance and property studied), either from the article or its abstract,

depending upon the subject and on the availability of the original. This

material becomes part of the computerized CTDC Abstracts Data Base.

This data base is the ready reference used in the Center when

evaluations of data are made. In addition, it is used to answer questions

from the public.

All of the Abstracts Data Base since 1970 is machine-readable. During

the year new programs have been written for processing the input. The

programs have been tested extensively and are being used in a production

mode. They have also been used to prepare indexes for the Bulletin of

Chemical Thermodynamics. CTDC has processed the material for the inorganic

index (prepared here), the organic index (prepared at Texam A&M Univ.), and

the organic mixture index (prepared at Univ. Paris) into a form that can be

handled by the index formatting programs of the Bulletin. The programs used

here have also been supplied to the editor of the Bulletin who plans to do

the entire processing task next year.

53
6 . PUBLICATIONS

(a) Publications of Past Year

Churney, K.L., E.S. Domalski, A.E. Ledford, Jr., J.C. Colbert, S.S. Bruce,

T.J. Buckley, and M.L. Reilly, "Assessing the Credibility of the

Calorific Value of Municipal Solid Waste", Proceedings of the 1986

National Waste Processing Conference, ASME, New York, 1986.

Ditmars, D.A., Plint, C.A. and Shukla, R.C., "Aluminum (I): Measurement of the Relative Enthalpy from 273 to 929 K; Derivation of Thermodynamic Functions for Al(s) frod 0 K to Its Melting Point", Int. J,

Thermophysics 6, M95 (1985).

Domalski, E.S., Churney, K.L. , Ledford, A.E., Bruce, S.S., Buckley, T.J.,

Parris, R., and Chesler, S.N., "Monitoring the Fate of Chlorine from

MSW Sampling through Combustion", Proceedings of the EPRI Seminar on Municipal Solid Waste as a Utility Fuel, EPRI, Palo Alto, CA, (1986),

Upp.

Domalski, E.S., Churney, K.L., Ledford, A,E.,Jr. and Reilly, M.L., "MSW

Calorimetry", Mechanical Engineering 108 , 32 (August, 1986).

Domalski, E.S., A.E. Ledford, Jr., S.S. Bruce, and K.L. Churney, "The

Chlorine Content of Municipal Solid Waste from Baltimore County, Maryland,

and Brooklyn, New York", Proceedings of the 1986 National Waste Processing

Conference, ASME, New York, NY, 1986.

Domalski, E.S., "NBS Research Program in Municipal Solid Waste Combustion",

Proceedings of the Biofuels and Municipal Waste Technology Division, U.S.

Department of Energy, 1986, 28 pp.

Evans, W.H., Grimes, J.J., Jobe, T.L., Young, N.W., Foreman, R. , Thompson, R.C.

and Seymour, C.L., "Substance - Property Index Section III. Inorganic

Substances", Bull. Chem. Thermodynamics, pp 219-286 (1983).

Evans, W.H., Grimes, J.J., Jobe, T.L., Young, N.W., Foreman, R., Thomspon,

R.C., and Seymour, C.L. "Substance - Property Index Section III. Inorganic

Substances", Bull. Chem. Thermodynamics, 26, pp 4?3“5^2 (1983).

Gajewski, E., Goldberg, R.N. and Steckler, D.K. "Thermodynamics of the

Conversion of Fumarate to L(-)Malate", Biophys. Chem., 2£, 187 (1985).

Garvin, D., Domalski, E.S., Wilhoit, R.C., Somayajulu, G.R., and Marsh, K.N.,

"Physical Properties of Pure Components of Natural Gas", in 'Gas

Quality', van Rossora, G.J., editor, Elsevier Science Publ., Amsterdam,

1986, p.59.

Garvin, D. and Parker, V.B., "CODATA Chemical Thermodynamic Data Bases for

Science and Technology", in 'Scientific Program and Abstracts, Tenth

International CODATA Conference', CODATA Bull, ^ ^8 (1986),

Garvin, D., and White, H.J., Jr., "Comprehensive, Consistent Thermodynamic

Tables", in 'Thermodynamic Databases', CODATA Bull 58, 1, (1986).

54
Goldberg, R.N., Gajewski, E., Steckler, D.K., and Tewari, Y.B.,

"Thermodynamics of the Conversion of Aqueous l-Aspartic Acid to

Fumaric Acid and Ammonia", Biophys. Chem. 2£, 13 (1986).

Goldberg, R.N. and Parker, V.B., "Thermodynamics of Solution of S02(g) in

Water and of Aqueous Sulfur Dioxide Solutions", J. Res. NBS, 9£, 3^1

(1985).

Johnson, W.H. and Prosen, E.J., "Determination of Enthalpies of Combustion and

Formation of Substituted Triazines in an Adiabatic Bomb Calorimeter",

J. Res. NBS, 90, 295 (1985).

Karpas, Z. , Stevens W.J. Buckley, T.J. and Metz, R. , "The Proton Affinity and

Gas Phase Ion Chemistry of Methyl Isocyanate, Methyl Isothiocyanate and

Methyl Theocyante" , J. Phys, Chem., 527^ (1985).

Kirchhoff, W.H., Chambers, G.P., Fine, J., "An Analytical Expression for

Describing Auger Profile Shapes of Interfaces.", J. Vac. Sci. Tech. AM,

1666 (1986).

Kirchhoff, W.H., "A National Program of Measurement Services and Standards

for Biotechnology at the National Bureau of Standards, Planning Report

22 (Revised)", February, 1986.

Kirchoff, W.H. "Who Needs Standards," Chemtech 16, 280 (1986).

Kirklin, D.R. and Domalski, E.S., "Estimation Methods and Combustion

Calorimetry on Organic Phosphorus Compounds", Proceedings of the 1985

Scientific Conference on Chemical Defense Research U.S Army, Research

Directorate, CRD&EC Aberdeen Proving Ground, 1986.

Miller, M.M., Wasik, S.P., Guang, G.L. Shiu, W.Y. and MacKay, D., "Relations

Between Octanol-Water Partition Coefficients, Aqueous Solubility and

Biocentration Factors", Enviromental Science and Technology, 1^, 522

(1985)

Neumann, D.B. "Data Base Management Systems, Part I. A Quick Overview",

Non Bibliography Data Banks in Science and Technology, S. Schwarz, D.G.

Watson , 0. Alvfeldt, eds. ICSU Press, 1985, p. 139.

Neumann, D.B., "Data Base Management Systems, Part II, An Application to

Scientific Technical Data and its Associated Bibliographic Data",

Non-Bibiographic Data in Science and Technology, S. Schwarz, D.G.

Watson, 0. Alvfeldt, Eds., ICSU Press, 1985, p. 153.

Owens, J.W., Wasik, S.P. and DeVoe, H. , "Aqueous Solubilities and Enthalpies

of Solution of n-Alkylbenzenes" , J. Chem. Eng. Data, M7 (1986)

Savage, H. , "Repulsive Regularities of Water in Ices and Crystalline

Hydrates", Nature 322 , 717 (1986).

Schwarz, F.P. "Biological Standard Reference Materials for Calibration of

Differential Scanning Calorimeters: Di-alklyl-Phosphatidylchol ine in

Water Solutions," Thermochim. Acta 107, 3M7 (1986).

55
Shukla, R.C., Flint, C.A. and Dittnars, D.Ao, ”Aluminum( IDs Derivation of

CyO from Cp and Comparison to CyO Calculated from Anharmonic Models'*,

Int. J. Thermophysics, 6, 517 (1985).

Steckler, D.K., Goldberg, R.N., Tewari, Y.B., Buckley, T.J. "High Precision

Microcaloriraetry. Apparatus, Procedures, and Biochemical Applications"

J. Res, NBS 91, 113 (1986).

Steckler, D.K., Goldberg, R.N., Buckley, T.S. "Computer Software for

Acquisition and Treatment of Calorimetric Data", NBS Tech Note 1224,

U.S. Government Printing Office, Washington, D.C, (1986).

Tewari, Y.B. and Goldberg, R.N., "An Investigation of the Equilibria Between

Aqueous Ribose, Ribulose, and Arabinose", Biophys. Chem. 22, 197 (1985)

Tewari, Y.B., Steckler, D.S. and Goldberg, R.N., "Thermodynamics of the

Conversion of Aqueous Xylose to Xylulose", Biophys. Chem. 22, 18

(1985).

Weber, I.T. and Steitz, T.A., "The Crystallization of rec A protein from

proteus mirabilis , J. Mol. Bio. 188 , 109 (1986).

Wlodawer, A., "A Facility for Data Collection and Processing at the National

Bureau of Standards Reactor", in Methods in Enzymology, H.W. Wyckoff,

C.H.W. Hirs, and S.N. Timasheff, eds.. Academic Press; New York, 114

,

551 (1988).

Wlodawer, A., Borkakoti, N. , Moss, D.S. and Hawkin, B. , "Comparison of Two

Independently Refined Models of Ribonuclease A", Acta Cryst., B42 , 379

(1986).

56
(b) Publications in Progress

Bickham, D.M., Neumann. D.B. , "Setky-Getky User's Manual", NBS-IR,

( in press)

.

Bickham, D.M., Neumann D.B., "Setky-Getky . A Keyed Access System for the

HP-1000." Proc. INTEREX North Am. Conf., (in press).

Bickham, D.M., "User Manual for the Chemical Thermodynamics Data Center

Hp-1000 mini-computer", NBS-IR (1986"), (in press).

Chase, M.W., Davies, C.A, Downey, J.Rv, Frurip, D.J., McDonald,

R.A., and Syvervd, A.N., 'JANAF Thermochemical Tables, Third Edition,

Phys. Chem. Ref. Data, 1_U, Supplement No. 1, 1985, (in press).

Churney, K.L., Ledford, A.E., Jr., Reilly, M.L., and Domalski, E.S.,

"A Multi-Kilogram Capacity Calorimeter for Heterogeneous Materials",

J Res NBS (in press).

Colbert, J.C. Domalski, E.S., and Coxon, B., "Enthalpies of Combustion of

D-Ribose and 2-Deoxy-D-ribose, J. Chem. Thermodynamics, (in press).

Ditmars, D.A., "Drop Calorimetry above 300 K" , McGraw-Hill/CINDAS Data Series

on Material Porperties, Chap 13, Compendium of Thermophysical Property

Measurement Methods, Vol. I, Plenum Publishing Corporation, 1986,

(in press)

.

Domalski, E.S., Churney, K.L. Ledford, A.E., Jr., Bruce, S.S., "Monitoring

the Fate of Chlorine from MSW Sampling Through Combustion, Part I: Analysis of the Waste Stream for Chlorine", Chemosphere (in press).

Domalski, E.S., Churney, K.L., Ledford, A.E, Jr., Bruce, S.S., Buckley, T.J.,

Parris, R.M., and Chesler, S.N., "Monitoring the Fate of Chlorine from

MSW Sampling through Combustion, Part II: Combustion Studies",

Chemosphere (in press)

Domalski, E.S., and Hearing, E.D., ^"Estimation of Thermodynamic Properties of

Hydrocarbons at 298. 15K", J. Phys. & Chem. Ref. Data, (submitted).

Domalski, E.S., Jobe, T.L., Jr., and Milne, T.A., "Thermodynamic Data for

Biomass Conversion and Waste Incineration", (submitted).

Garvin, D., Parker, V.B., and White, H.J., Jr., editors ’CODATA

Thermodynamic Tables; Selections for Some Compounds of Calcium and

Related Mixtures. (A Prototype Set of Tables)', CODATA Special Report,

1986, 370 pp., (in press).

Garvin, D., Schumm, R.H., Parker, V.B., and Nuttall, R.L., "Thermochemical

Properties at 0 and 298. 15K", in 'CODATA Thermodynamic Tables:

Selections for Some Compounds of Calcium and Related Mixtures. (A

Prototype Set of Tables).' CODATA Special Report, 1986, section 6.2, pg.

100-196, and section 7.1, pg 216-318, (in press).

57
Gurvich, L.V., Yungman, V.S., Chase, M.W., and Bergman, G.k,, "Thermodynamic

Properties of Individual Substances", in 'CODATA Thermodynamic Tables.

Selections for Some Compounds of Calcium and Related Mixtures. (A

Prototype Set of Tables).' CODATA Special Report, 1986, section 6.1,

pg. M2“179, (in press).

Gajewski, E., Steckler, D.K., Goldberg, R.N., "Thermodynamimcs of the

Hydrolysis of Adenosine 5' ~ Triphosphate to Adenosine 5'~ Diphosphate,"

J. Biol. Chem., (in press).

Harrison, R., "Sayres Equation is a Chernov Bound to Maximum Entropy", Acta

Crystallographica, (in press).

Miller, M., Apella, E., Schwarz, F.P., Kirchhoff, W., Sussman, J., "Possible

Conformations in Solution for Synthetic Quasi palindromic DNA

Sequences.", (submitted).

Parker, V. B. , Evans, W.H., Nuttall, R.L., "The Thermochemical Measurements

on Rubidium Compounds: A Comparison of Measured Values with those

Predicted from the NBS Tables of Chemical Thermodynamic Properties", J. Phys, Chem. Ref. Data, (in press).

Raghavan, N.V. and Wlodawer, A., "Neutron Crystallography of Proteins,"

Methods in Experimental Physics, (in press).

Roy, S., Weinstein, S. , Borah, S. , Nickol, L. , Appella, E. , Sussman, J.L.,

Miller, M, Shindo, H. Cohen, J.S., "The Mechanism of Olignonucleotide

Loop Formation Solution", Biochem., (in press).

Savage, H. and Wlodawer, A., "Determination of Water Structure Around

Biomolecules Using X-ray and Neutron Diffraction Methods", Methods in

Enzymology (Biomembranes), (in press).

Savage, H. "Water Structure in Vitamin B-12 Coenzyme Crystals II, Biophysical

Journal", (in press).

Savage, H. "Water Structure in Crystalline Solids: Ices to Proteins Water

Reviews", (in press).

Smith-Magowan, D. , Garvin D., Parker, V.B., Nuttall, R.L., and Staples, B.R.,

"The Aqueous System CaCl 2 H2 O", in 'CODATA Thermodynamic Tables.

Selections for Some Compounds of Calcium and Related Mixtures. (A

Prototypoe Set of Tables).' CODATA Special Repcrt, 1986, section 6.5,

pg. 216 -243 , section 7.3. pg. 326-342, (in press).

Smith-Magowan, D., editor, "Bibliographies of Industrial Interest:

Thermodynamic Measurements on the Systems CO2 -H2 O, CUCI-H2

O, NH

2 “H20 , ZnCl 2“H20 , H

2 P 02|-H 20 ." NBS Special Publication (in press).

Svensson, A., Sjolin, L. Gilliland, G.L., Finzel, B.C., Wlodawer, A., "Multiple

Conformations of Amino Acid Residues in Ribonuclease A", (submitted).

Tewari, Y.B., and Goldberg, R.N., "Thermodynamics of Carbohydrate

Isomerization Reactions: The Conversion of Aqueous Allose to Psicose",

Biophys. Chem., (in press).

58
Tewari, Y.B. , and Goldberg, R.N. "An Equilibrium Study of the Conversion of

L-Phenylalanine to Trans-Cinnamic Acid and Ammonia.", J. Phys Chem. , (in

press)

.

Weber, I.T., "The Structure of Catabolite Gene Activator Protein Crystallized

with Cyclic Amp" in Methods of Enzymology (Hormone Action) Cyclic

Nucleotide Action and Degradation, J.D. Corbin and R.A. Johnson, eds,

(in press)

.

• Weber, I.T., Steitz, T.A., Bubis, B. Taylor, S.S., "Predicted Structures of

the c AMP Bindine Domains of the Type I and II Regulatory Subunits of a

c AMP-dependent Protein Kinase, (submitted).

Wlodawer, A., Deisenhofer, J., Huber, R., "Comparison of Two Highly Refined

Structures of Bovine Pancreatic Trypsin Inhibitor", J. Mol. Biol.,

(in press)

.

Wlodawer, A. and SJolin, L. "Experience with the Use of a Neutron Data

Collection Facility Equipped with an Area Detector.", Les Editions de

Physique, (in press).

Zielinski, W.L., Miller, M.M., Ulma, G. and Wasik, S.P., "GLC Separation of

Polychlorinated Biphenyl Isomers Between a Nematic Liquid Phase and a Non-Polar Base", Analytical Chem., (in press).

59
7 « Talks

Abramowitz, S. , "Thermodynamic Properties of High Temperature Materials", Air

Space Technology Center, Albuquerque, NM, November 19, 1985.

Abramowitz, S., "Biochemical Research in Support of NBS* Biotechnology

Program", Center for Chemical Engineering, Boulder, CO, September 15,

1986.

Abramowitz, S. , "NBS* Biotechnology Program", Thermochemical Brigham Young

University, Provo, UT, 8M602, September 24, 1986.

Bickham, D.M., "SETKY-GETKY, A Keyed Access System for the HP-1000", INTEREX

North Am. Conf., Detroit, MI, September 28-October 3, 1986.

Buckley, T.J., "Formation and Reactions of Hydrocarbon Ions Under Ionospheric

Conditions." The 1985 AFOSR Scientific Conference on Laser-Material

Interaction in Obscuration Research, Albuquerque, NM, November 19, 1985.

Buckley, T.J., "Design of a Real Time Data Acquisition for Combustion

Calorimetry", 41®^ Annual Calorimetry Conference, Somerset, NJ, August

18, 1986.

Chase, M.W., "JANAF Thermochemical Tables", AFOSR/AFRPL Rocket Propulsion

Research Meeting, Edwards Air Force Base, CA, September 9“11, 1986.

Churney, K.L., "Assessing the Calorific Value of Municipal Solid Waste",

Twelfth National Waste Processing Conference, Denver, CO, June 4, 1986.

Churney, K.L., "Design and Performance Tests of a Multi-kilogram Capacity Flow

Calorimeter", 41^^ Annual Calorimetry Conference, Somerset, NJ, August 18,

1986.

Domalski, E.S., "The Chlorine Content of Municipal Solid Waste", Derwood

Lions Club, Derwood MD , May 20, 1986.

Ditmars, D.A., "Heat Capacity of Solid Calcium; a Tour de Force of

Equilibrium Macrocalorimetry" , Chemical Thermodynamics Seminar, NBS,

Gaithersburg, MD, September, 30, 1986.

Domalski, E.S., "The Chlorine Content of Municipal Solid Waste from Baltimore

County, MD, and Brooklyn, NY", Twelfth National Waste Processing

Conference, Denver, CO, June 4, 1986.

Domalski, E.S., "Monitoring the Fate of Chlorine from MSW Sampling through

Combustion", DOE/EPRI Seminar on Municipal Solid Waste as a Utility

Fuel, Madison, WI, November 22, 1985.

Domalski, E.S., "A Status Report of Research Activities on the Combustion

Calorimetry of MSW", Solar Energy Research Institute (SERI), June, 4,

1986.

Domalski, E.S., "Monitoring the Fate of Chlorine from MSW Sampling through

Combustion", Acid Gas and Dioxin Control for Waste-to-Energy Facilities

Conference, Hyatt Regency, Crystal City, VA, November 26, 1985.

60
Gajewski, E., ’’The Enthalpy of Hydrolysis of Adenosine 5’ ~ Triphosphate”,

76^*^ Annual Meeting of the American Society of Biological Chemists,

Washington, DC, June 12, 1986.

Gajewski, E., "Thermodynamics of the Conversion of L-Aspartate to Fumarate

and Ammonia”, International Symp>osium on HPLC of Proteins, Peptides,

and Polynucleotides”, Toronto, Ontario, November 6, 1985.

Garvin, D., "Physical Properties of Pure Components of Natural Gas”, 1^^

International Congress on Gas Quality—Specification and Measurement of

Physical and Chemical Properties of Natural Gas, Groningen, the

Netherlands, April 22-25, 1986. *

Goldberg, R.N., "A Computerized Database of Activity and Osmotic

Coefficients", Nuclear Regulatory Commission, Silver Spring, MD,

December 1985.

Goldberg, R.N., "A Computerized Database of Activity and Osmotic

Coefficients", Office of Standards Reference Data Advisory Panel,

December, 1985.

Goldberg, R.N., "Thermodynamics of Enzyme-Catalyzed Reactions”, Chemical

Thermodynamics Division, NBS, Gaithersburg, MD, March, 1986.

Goldberg, R.N., "Thermodynamics of Enzyme-Catalyzed Reactions", Laboratory

of Metabolism, NIH, Rockville, MD, May, 1986,

Goldberg, R.N., "Thermodynamics of Enzyme-Catalyzed Reactions”,

Laboratory of Metabolism, NIH, Rockville, MD, May, 1986.

Goldberg, R.N. , "Current Research in Chemical Thermodynamics", ICI, Runcorn,

Cheshire, United Kingdom, July 7, 1986.

Goldberg, R.N., "Thermodynamics of Enzyme-Catalyzed Reactions”, University of

Newcastle-upon-Tyne, United Kingdom, July 9, 1986.

Goldberg, R.N., "GAMPHI-A Database of Activity and Osmotic Coefficients",

University of Newcastle-upon-Tyne, United Kingdom, July 10, 1986.

Goldberg, R.N., "Thermodynamics of Enzyme-Catalyzed Reactions”, University of

Glasgow, United Kingdom, July 11, 1986.

Goldberg, R.N., "Thermodynamics of the Conversion of L-Aspartate to Fumarate

and Ammonia”, 9^*^ lUPAC Thermodynamics conference, Lisbon, Portugal,

July 18, 1986.

Goldberg, R.N., "The Enthalpy of Hydrolysis of Adenosine 5 '“Triphosphate"

,

9

tn Thermodynamics Conference, Lisbon, Portugal, July 18, 1986.

Goldberg, R.N., "The Enthalpy of Hydrolysis of Adenosine 5 ' “Triphosphate"

,

Ml^^ Calorimetry Conference, Somerset, NJ, August 21, 1986.

61
Goldberg, R.N., "Thermodynamics of the Conversion L-Plenylalanine to

Trans-Cinnamic Acid and Ammonia", ACS Middle Atlantic Regional Meeting,

Baltimore, MD, September 2, 1986.

Goldberg, R.N., "Thermodynamics of the Hydrolysis of Adenosine

5 '“Triphosphate", ACS Middle Atlantic Regional Meeting, Baltimore, MD,

September 2, 1986.

Harrison, R. , "A Common Sense Guide to Maximum Entropy", Mid“Atlantlc

Protein Cystallography Workshop, NBS, May 15-17, 1986.

Kirchhoff, W.H., "An Analysis Program, for the Characterization of Interface

Profile Shapes", 8^*^ Symposium on Applied Surface Analysis, University

of Dayton, Dayton, OH, June 1986.

Kirchhoff, W.H., "A Computer Program for Describing the Denaturation of

Biopolymers, as Measured by Differential Scanning Calorimetry, in Terms

of a Two State Model", 41®^ Calorimetry Conference, Somerset, NJ, August

22, 1986.

Kirklin, D.R., "Estimation Methods and Combustion Calorimetry on Organic

Phosphorus Compounds", 1985 Scientific Conference on Chemical Defense

Research, Aberdeen Proving Ground, MD, November 22, 1985.

Kirklin, D.R., "Enthalpies of Formation of Organic Phosphorus Compounds",

41®^ Annual Calorimetry Conference, Somerset, NJ, August 21, 1986.

Miller, M., "Oligomers of DNA", Mid-Atlantic Protein Crystallography

Workshop, NBS, May 15-17, 1986.

Neumann, D.B., "The Chemical Thermodynamics Data Center Bibliographic Data

Base System", Chemical Thermodynamics Division Seminar, April, 1986.

Newmann, D.B., "The Application of the IMAGE/1000 Database Management System

to Scientific Data", Baltimore-Washington HP-1000 Users Group,

Baltimore, MD, November 15, 1985.

Parker, V.B., "CODATA Chemical Thermodynamic Data Bases for Science and

Technology", Tenth International CODATA Conference, July 15, 1986,

Ottawa, Canada.

Smith-Magowan , D. , "A Database of Thermodynamic Properties of Aqueous

Electrolyte Solutions with Computational Procedures for Industrial

Applications", AIChE National Meeting, Chicago, IL, November 1985.

Smith-Magowan, D., "Effects of Temperature, Pressure and Composition on the

Thermodynammic Properties of Electrolytes", International Association

for Properties of Steam, Dusseldorf, W. Germany, Sept 22-26, 1986.

Tewari , Y.B., "Thermodynamic Investigations of Reactions Catalyzed by Glucose

Isomerase", Indian Institute of Technology, New Delhi, India, October

29, 1985.

Tewari, Y.B., "Thermodynamic Investigations of Enzyme Catalyzed Reactions",

Indian Institute of Technology, Bombay, India, November, 21, 1985.

62
Tewari, Y.B., "Thermodynamics of Carbohydrate Isomerization Reactions:

Conversion of Aqueous Allose to Psicose", Calorimetry Conference,

Somerset, NJ, August 21, 1986.

Tewari, Y.B., "Thermodynamics of the Conversion of L-phenylalanine to

Trans-Cinnamic Acid and Ammonia", 41®^ Calorimetry Conference, Somerset,

NJ, August 21, 1986.

Tewari, Y.B., "Thermodynamics of Carbohydrate Isomerization Reactions: The

Conversion of Aqueous Allose to Psicose", ACS Middle Atlantic Regional

Meeting, Baltimore, MD, September 2, 1986.

Weber, I.T., "The Analysis of Protein Structure from Crystallographic Data".

The Structure of Catabolite Gene'Activator Protein and its Complex with

DNA", Course on Protein Structure and Function, Les Diablerets,

Switzerland, September 30 to October 3» 1985.

Weber, I.T., "Model for the Complex of Catabolite Gene Activator Protein and

Its Site in Lac Operon" , Series on the Relation between DNA Structures

and their Interactions, NIH, Bethesda, MD, March 19, 1986.

Weber, I.T., "The Structure of a Mutant of Catabolite Gene Activator

Protein.", Mid-Atlantic Protein Crystallography Workshop, NBS,

Gaithersburg, MD, May 15-17, 1986.

Weber, I.T., "The Crystal Structure of a Mutant of Catabolite Gene

Activator Protein.", Gordon Conference: Diffraction Methods in Molecular

Biology, New Hampshire, June 30-July 4, 1986.

Wlodawer, A., "A Novel Method for the Determination of Solvent Structure in

Protein Crystals", Max-Planck-Institut , Munich, West Germany, January

28, 1986.

Wlodawer, A., "High Resolution Studies of Proteins Using X-ray and Neutron

Diffraction", University of Washington, Seattle, WA, June, 3. 1986,

Wlodawer, A., "Bound Solvent in Proteins: Improvement of Fourier Maps by

Protein Averaging Combined with Flattening of the Solvent", Gordon

Research Conference, Andover, NH, June 30, 1986.

Wlodawer, A., "Bound Solvent in Proteins - a Novel Technique for its Analysis",

Tenth European Crystallographic Meeting, Wroclaw, Poland, August 5,

1986.

Wlodawer, A., "High Resolution Refinement of BPTI and Ribonulcease"

,

Department of Crystallography, Birkbeck College, University of London,

England, August 15, 1986.

Wlodawer, A., "X-ray and Neutron Diffraction Studies of Proteins and Nucleic

Acids", NBS Staff Research Seminar, September 5, 1986.

63
8. Chemical Thermodynamics Division Seminars

Kamlet, M.J., Navel Surface Weapons Center, Silver Spring, MD, *'A General

Equation for Correlation and Prediction of Solute““Solvent Interaction

in Chemical and Biological Systems”, October 1, 1985.

* Bott, R. , Genentech, Inc. South San Franciso, CA, "Protein Engineering,

Modification of the Oxidative Stability of Subtilisin", October 18,

1985.

Ditmars, D.A., NBS, Gaithersburg, MD, "Heat Capacity of Solid Calcium: a Tour de Force of Macrocalorimetry", September 30, 1986,

* O’Leary, T.J., NIH, Bethesda, MD, "Spectroscopic and Calorimetric Studies

of Biomembranes", October 2M, 1985.

* Osman, R., Department of Physiology and Biophysics, New York, NY, "A New

Mechanism of Action of Superoxide Dismutase", November 7, 1985.

* Rein, R., Department of Biophysics, Roswell Park Memorial Institute

Buffalo, NY, "Multistep Modeling of Bioactive polypeptides in

3“Dimensions" , November 14, 1985.

* Hyde, C., NIH, Bethesda, MD, "Three Dimensional Structure of Aspartate

Aminotransferase and Substrate Complexes", December 18, 1985.

Thompson, P.T., Chemistry Department, Swarthmore College, Swarthmore, PA,

"Progress Towards the Development of Simple Potential Functions for

Solute-Solute Interactions in Non-electrolyte Aqueous Solution",

January 13, 1986.

* Goldberg, R.N., NBS, Gaithersburg, MD, "Thermodynamics of Enzyme Catalyzed

Reactions", February 21, 1986.

* Wlodawer, A., NBS, Gaithersburg, MD, "Structure of a ’Standard* Protein

Bovine Pancreatic Trypsin Inhibitor at High Resolution", February 28,

1986.

Neumann, D., NBS, Gaithersburg, MD, "A Bibliographic Database for the

HP-1000 Mini-Computer", March 5, 1986.

Roy, R., Drury College, Springfield, MO, "Thermodynamics of Mixtures of

Strong Electrolytes: Applications of Pitzer’s Equations", March 20,

1986.

* Gitomer, W., NIH, Bethesda, MD, "The Estimation of the Free Mitochondrial

Ca^"^ Concentration in Vivo", April 15, 1986.

* Zeyfus, M., Department of Biological Chemistry, Pennsylvania State

University, University Park, PA, "Compact Domains of Proteins", April

17, 1986.

64
Pember, S. , Department of Chemistry, Pennsylvania State University,

University Park, PA, "Mechanism and Structure of Chromobacterium

Violaceum Phenyl Alanine Hydroxylase”, April 22, 1986.

Harman, J.G., NIH, Bethesda, MD, "Structure - Function Analysis of Cylic

AMP Receptor Protein", May 12, 1986.

McKenney, K., NIH, Bethesda, MD, "Protein Structure Function Studies Using

Synthetic Oligonucleotides", May 1M, 1986.

Tweedy, N.B., Department of Chemistry, Pennsylvania State University,

University Park, PA, "Effects of Point Mutations on Protein Folding",

May 21, 1986.

Biotechnology Seminars
9. TECHNICAL AND PROFESSIONAL

COMMITTEE PARTICIPATION AND LEADERSHIP

Abramowitz, S.

Member, ASTM Commitee E~38 on Resource Recovery, Subcommittee E38.01

Energy

Bickham, D.

Member, Baltimore-Washington HP~1000 Users Group

Chase , M

Vice-chairman, ASTM Committee E-27 on Hazard Potential of Chemicals

Consultant, CODATA Task Group on Chemical Thermodynamic Tables,

Corresponding member, Engineering Science Data Unit - Physical Data

and Reaction Committee

Churney, K.L.

Member, ASTM Committee E-37 on Thermal Measurements

Member, ASTM Committee on Hazard Potential of Chemicals, Subcommittee

E-27. 02 on Thermal Stability

Member, ASTM Committee E -38 on Resource Recovery

Colbert, J.C. . Member, ASTM Committee E -38 on Resource Recovery, Subcommittee E38.01

Energy

Member, ASTM Committee D-05 on Coal and Coke

Ditmars, D.A.

Member, ASTM Committee E37.05 on Thermal Measurements/Thermophysical

Properties working group I (Thermodynamics) Task Group 1.5 (Drop

Calorimetry), 1.6 (Adiabatic Calorimetry)

Division Safety Officer

Member, Standards Committee, U.S. Calorimetry Conference

Domalski, E.S.

Member, ASTM Committee E-27 on Hazard Potential of Chemicals, Subcommittee

E-27. 07 Computational Methods

Member, ASME Research Committee for Industrial and Municipal Wastes

Member, ASTM Committee E -38 on Resource Recovery, Subcommittee

3~38.01 Energy

66
Garvin, D.

Secretary, CODATA Task Group on Chemical Thermodynamic Tables

Member, ASTM Committee E -38 on Resource Recovery

Member, ASTM Committee E-27 Hazard Potential of Chemicals

Kirchoff, W.H.

Immediate Past Chairman, ASTM Committee E-M7 on Biological Effects

and Environmental Fate

Member, ASTM Committee E-48 on Biotechnology

Titular member, lUPAC Commission I.lo on Physicochemical Symbols,

Terminology and Units

Kirklln, D.R.

Member, ASTM Committee E~38 on Resource Recovery, Subcommittee

E-38.01 on Energy, Subcommittee E-38 . 02 on Research

Director, U.S. Calorimetry Conference

Neumann, D.

Member, Hewlett-Packard HP-1000 International Users Group

Member, Baltimore-Washington HP-1000 Users Group

Parker, V. B. Consultant, IAEA Committee on Chemical Thermodynamics of Actinide

Elements and Compounds,

Member, Subcommittee lAEA.WG.OI Actinide Halide Thermodynamics.

Corresponding member, CODATA Task Group on Chemical Thermodynamic

Tables

Member, Chemical Thermodynamimcs Advisory Canmittee on Aqueous

Solutions Data Base, (Lawrence Berkeley Laboratories, Sidney

Phillips)

Smi th-Ma gowan , D

.

Organizing Committee of the ’International Conference on Thermodynamics of

Aqueous Solutions with Industrial Applications’, Airlie House, May

1987.,

Member, International Association for the Properties of Steam

Wlodawer, A.

Treasurer, Neutron Special Interest Group of the American Crystallographic

Association

Member, Apparatus and Standards Committee, American Crystallographic

Association

67
10„ PROFESSIONAL INTERACTIONS, CONSULTING

AND ADVISORY SERVICES

Abramowitz, S.

Collaborated with I.W., Levin, National Institute of Arthritis and

Metabolic Disease, NIH, on vibrational analysis of small molecules

and some biological species.

Formulated cooperative research program on high temperature

thermodynamics with AFOSR.

Interacted with the following agencies and organizations regarding

the NBS program in Biotechnology: National Aeronautic and Space

Administration (NASA) , National Academy of Science (NAS) , National

Science Foundation (NSF), Office of Technology Assessment (OTA).

Chase, M.

Reviewed and planned for physical property data issued by

Engineering Science Data Unit.

Participated In the development of ASTM Standard on "Calculation of

Hazard Potential Figures of Merit for Thermally Unstable Materials"

prepared by ASTM. Committee E*-27 on Hazard Potential for

Chemicals.

Supplied thermal functions to the Therdynamic Research Center, Texas

A & M University, for inclusion in the TRC Hydrocarbon and

Non-hydrocarbon Tables.

Collaborated with AIP on the design and publication of the JANAF

Tables, 3rd edition.

Prepared tables of thermal functions for the CODATA Thermodynamic

Tables and for CODATA Key Values for Thermodynamics, and

participated in meetings of the CODATA Task Group on Chemical

Thermodynamic Tables.

Interacted to obtain data needed for development of theoretical

concepts used in the JANAF Tables with J.L. Haas, Jr, United States

Geological Survey (USGS) , T. Chart, & A. Dinsdale, NPL, U.K., M.H.

Rand, AERE, Harwell, U.K., L. Brewer, U. CA, Berkley, P.F. Bernath,

AZ State U., and D.O. Harris, U. CA, Santa Barbara, CA.

Reviewed an extensive series of articles on Isomer Group Thermodynamics

(R.A. Alberty, MIT).

Churney , K.L.

Interacted with R. Wingender of the Analytical Chemistry Lab of

Argonne National Laboratory, Argonne, IL on analysis of effluent

fractions from combustion measurements for chlorinated dioxins and

related compounds.

68
Colbert, J.C.

Interacted with ASTM Committee D-05 on Coal and Coke and its

Subcommittee 21.02 on Methods of Analysis. Membership and active

participation with subcommittee members on the evaluation of

calorimetric procedures for determining the calorific value of coal

and coke.

Cooperated in research with B. Coxon of the NBS Organic Analytical

Research Division on bomb calorimetric and NMR studies of D~ribose

and 2-deoxy-D-ribose.

Ditmars, D.

Cooperated with R.A. Robie of the U.S. Geological Survey, Reston,

VA, on preparing a sample of pure calcium and measuring the heat

capacity of the solid phases from MK to the melting point, 1112Kc

Interacted with Commission on Standardization of Thermophysical

Property Measurements of the European Thermophysical Properties

Union. This Commission is sponsoring and coordinating the assembly

of a two- volume compendium of apparatuses and techniques for the

measurement of thermophysical properties. One chapter has appeared

in press on a survey of high temperature drop calorimetry. Another

chapter on hardware design is in preparation.

Cooperated with C.A. Plint, Physics Department, Brock University,

Ontario, Canada, on measurement of the high- temperature heat capacity

of pure copper.

Cooperated with the investigator on U .S. -Yugoslav cooperative research

project being carried out at NBS (Chemical Thermodynamics Division)

and at Boris Kidric Institute,, Belgrade (Institute for Thermal

Engineering and Energy Research).

Provided advisory service to U.S. Naval Weapons Ordinance Center, Crane,

Indiana on calorimetry hardware, techniques for studying low-level

degrading reactions in solid propellants and explosives.

Domalski, E.S.

Cooperated with engineers involved in solid waste disposal, solid

waste processing, and resource recovery from the ASTM Committee E -38

on Resource Recovery and The ASME Research Committee on Industrial

and Municipal Wastes concerning combustion characteristics of waste

materials.

Participated in the USUK collaboration for Waste Combustion.

Areas of interest are ; (1) chlorine content analysis of municipal

solid waste, (2) calorific value data derived from U.S. and U.K. one kilogram-capacity calorimeters , and (3) combustion studies on threshold conditions for the formation/ destruction of chlorinated

species.

Interacted with the U.S. Department of the Army, Chemical Research

and Development (CRDC), Aberdeen Proving Ground, Maryland to carry

out combustion calorimetry and develop estimation methods for organic

phosphorus compounds (CRDC) has continued in FY 1986.

69
Negotiated for the publication of a compilation entitled?

"Thermodynamics Data for Biomass Conversion and Waste Incineration",

prepared at NBS, compiled at the Solar Energy Research Institute, and

funded by DoE, as an ASME document.

Interacted with engineers from Combustion Engineering (J, Orcutt and

D, Borio) during a visit to the large sample flow calorimeter

facility and through discussion of plans for future research on monitoring chlorine during MSW combustion.

Gajewski, E.

Interacted with Anne Plant, Center for Analytical Chemistry,

purification of monoclonal antibodies,

Garvin, D.

Worked with CODATA on the preparation of thermodynamic data bases, jointly

with groups at AERE, Harwell, U.K., (M.H. Rand), LIPCM-ENSEEC,

Grenoble, France (I. Ansara), Univ. of Sussex, Brighton, UK, (J.B.

Pedley), and TERMOCENTER Akad. Nauk, Moscow, USSR (L.V. Gurvich, V.A.

Medvedev, V. Yungman), and US Geolog. Survey, Res ton, VA, USA (J.L,

Haas, Jr.).

Visited British Gas, London Research Station, London, U.K. (A,E.

Humphreys) regarding calorimeter design.

Selected values for properties of components of natural gas:

Thermodynamic Research Center, Texas A & M Univ., College Station,

TX, (K.N. Marsh, R. Wilhoit).

Participated in completion of the handbook for calculation of properties of natural gas for the International Group of Importers of

Liquified Natural Gas (GILGNL) , NBS, Boulder, CO, (D. Mann).

Interacted with international standards (Chemical) community. Observer at

lUPAC General Assembly, Lyons, France, Commission 1.3 [Nomenclature],

1.2 [Thermodynamics], 1.4 [Chemical Kinetics], and II. 3 [High

Temperature Chemistry].

Attended DOE Contractor's Meeting for Department of Energy on clean

up of coal combustion stack gases, assessment of industry needs.

Goldberg, R.N.

Met with Richard Veech, National Institutes of Health, general

discussions on the thermodynamics of enzyme-catalyzed reactions.

Met with Richard Virdins, University of Newcastle-upon-Tyne, United

Kingdom, to discuss possible work in the penicillinase reaction.

Met with Arthur Carrington, University of Newcastle-upon-Tyne, United

Kingdom, to discuss pH Standards.

Discussed with Yung-Chi Wu, Center of Analytical Chemistry, the

treatment of electrochemical data.

70
Kirchhoff, W.H.

Collaborated with I.W. Levin, et. al . Laboratory of Chemical Physics,

National Institute of Arthritis, Diabetes and Digestive and Kidney

Diseases on thermodynamic properties of lipids.

Worked with J.D. Fine, Surface Science Division, on the statistical

analysis of depth profile data.

Neumann, D.B.

Collaborated with Freeman, Oklahoma State Univ. on the publication of

the Bulletin of Chemical Thermodynamics.

« Interacted with A. Maczynski, Institute for Physical Chemistry,

Polish Academy of Sciences, Warsaw, Poland - Protocal for the

international exchange of chemical thermodynamic data - lUPAC

sponsored activity.

Participated in Task Group meetings at Ottawa, July 1986. CODATA

Task Group on Chemical Thermodynamics Tables.

Provided computer programs to Office of Stcindard Reference Data to

assist in the production of camera ready documents and tables, acted

as consultant for the planning of automation activities at NBS and

DOC.

Consulted with J.W. Gadzuk, Division 5^1, on graphics for

publication.

Consulted with D.J. Orser, Division 739, on presentation of topology

of phase diagrams.

Consulted with G. Klopman, Dept of Commerce, on oceanographic data

(Netherlands) to the NBS computer.

Parker, V.B.

Consulted with E. Busenberg and N. Plummer, USGS, Res ton, VA

concerning the thermochemistry of BaC03(cr) and the selection of the

"best values" for the enthalpy of formation at zero K; also

concerning Ba'*'^ (aq. std. state) and values for the enthalpy of

formation at 0 K and the entropy.

Consulted with John Haas, USGS Geological Survey, concerning the

thermochemical behavior of iron oxides.

Discussed with V. Medvedev, Institute for High Temperatures and I.

Khodakovsky, Vernadsky Institute for Geochemistry and Analytical

Chemistry, Moscow, the evaluation of the thermochemistry

of key iron compounds.

Held discussions on USA/USSR Science exchange: Exchange of data,

calculational methods and interpretations of data between the Chemical Thermodynamics Data Center and a similar group at the Institute

for High Temperatures, Moscow.

71
Collaborated with members of the CODATA Task Group on the

preparation of Chemical Thermodynamic Tables; Preparation of

thermodynamic data bases, jointly with groups at AERE, Harwell, U.K,,

(M.H. Rand), LIPCM-ENSEEG, Grenoble, France, (I. Ansara) , and

TERMOCENTER Akad. Nauk, Moscow, USSR, (L. V.Gurvich, V.A, Medvedev, V.

Yungman) , and USGS, Reston, VA, USA (J. Haas Jr,)

Held discussions, provided advice and guidance to Phillips,

Lawrence Berkeley Lab. and M. Siegel, Sandia National Lab. on the

need for and the construction of thermodynamic data bases for

modelling in geothermodynamic equilibrium calculation in aqueous

solutions.

Provided advice and guidance on handling uncertainties in thermodynamic

data to NRC, DOE, and USGS at a panel meeting Dec. 17, 1985 at

NRC Silver Spring, MD.

Collaborated with D.D Wagman, former NBS staff scientist, on chemical

thermodynamic key values and thermodynamic tables.

Schwarz, F.P.

Collaborated with I.W. Levin, Laboratory of Chemical Physics,

National Institute of Arthritis, Diabetes and Digestic and Kidney

Diseases on the thermal properties of lipids.

Collaborated with A. Shrake, Office of Biologies, FDA on the thermal

stability of serum albumen.

Smith-Magowan, D.

Collaborated with R.H. Wood, University of Delaware, on the development of

methods for the correlation and theoretical interpretation of the

thermodynamic properties of aqueous solutions at elevated temperatures

and pressures.

Interacted with S.L. Miller, Univ, of California, San Diego, on the

correlation of equilibria comprising the Krebs (tricarboxylic acid)

cycle and associated metabolic pathways. Joint manuscript is in

preparation.

Interacted with J.O.M. Levelt-Sengers , Thermophysics Div, NEL, NBS; on the

interpretation the properties of aqueous electrolytes near their

critical points.

Interacted with P.T. Thompson, Swarthmore College, on the calculation

of virial coefficients of small organic compounds in aqueous

solution.

Provided advice to Dewey, Reynolds Metals Co., Richmond, Va; on the

vapor pressure and enthalpy of concentrated NaOH solutions at

elevated temperatures.

Provided advice to J. Erwin, SWRI, San Antonio TX, on the electrical

conductivity of aqueous mixtures of CO2.

72
Provided advice to R.L. Truitt, Dallas TX, on the formulation of

colloidal suspensions of magnetic materials.

Provided advice to W. Kelly, Nuclear Regulatory Commission, on the

data for aqueous solutions used in codes to predict the stability of

nuclear waste storage deposits.

Tewari, Y.B.

Held discussion with and interacted with Dr. William Gitomer of the

Laboratory of Metobilism at NIH on the equilibrium measurement for

the process: hydrolysis of glucose 6-phosphate.

Weber, I.T.

Held discussions and interacted with Dr. Sancar Adhya, NIH, on the

crystallization and structural studies of ^ coli gal repressor.

Held discussions and interacted with Professor Herman Ammon,

Department of Chemistry, University of Maryland, on structural

studies of glutaminase-asparaginases from several bacterial sources.

Collaborated with Dr. Gary Gilliland, Genex Corporation, Gaithersburg,

MD, on data collection from crystals of catabolite gene activator

protein.

Interacted with Dr. Keith McKenny, NIH, on the crystal structures of

mutants of catabolite gene activator protein.

Interacted with Dr. Alan Peterkofsky, NIH, on the crystal structures

of several mutants of catabolite gene activator protein.

Interacted with Professor Thomas ^teitz. Department of Molecular

Biophysics and Biochemistry, Yale University, New Haven CT, on crystallization of rec A protein and on refinement of the structure

of catabolite gene activator protein.

Interacted with Professor Susan Taylor, Department of Chemistry,

University of California, San Diego CA, on the prediction of the

structure of the regulatory subunit of mammalian cAMP-dependant

protein kinase.

Interacted with Dr. Susan Wickner, NIH, on the crystallization of

’0* -protein that is required for transcription in phage X.

Wlodawer, A. Collaborated with Professor Robert Huber, Max Planck Institute,

Martinsried, West Germany, on the comparison of two crystal forms of

bovine pancreatic trypsin inhibitor.

Collaborated with Professor Lennart Sjolin, Chalmers Polytechnic,

Gothenburg, Sweden, on the structural investigations of ribonuclease

and bovine pancreatic trypsin inhibitor.

Collaborated with Dr. Franz Schmid, University of Regensburg, West

Germany, on crystallographic studies of porcine ribonuclease.

73
Collaborated with Dr. David Moss, University of London, England, on comparisons of independently refined structures of bovine

ribonuclease.

Collaborated with Professor Herman Ammon, University of Maryland, on crystallographic studies of glutaminase-asparaginases from several

bacterial sources.

Collaborated with Dr. Giuseppe Zaccai, Institute Laue-Langevin,

Grenoble, France, and Dr. Martin Gellert, NIH, Bethesda, MD, on the

low-angle neutron scattering studies of gyrase and gyrase-DNA com- plexes.

Collaborated with Dr. Ettore Appella, NIH, Bethesda, MD, on crystallization of DNA fragments.

Collaborated with Dr. Joyce Jentoft, Case Western University, OH, on crystallographic studies of the RNA-binding protein from the phage

pp12.

Collaborated with Dr. Gary Gilliland, Genex Corporation,

Gaithersburg, MD, on crystallographic studies of a sweet protein,

monellin, and on high resolution refinement of ribonuclease.

Collaborated with Dr. Matthew Pincus, Brooklyn Polytechnic, on crystallography of covalent complexes between ribonuclease and

nucleotides.

74
1 1 . VISITING SCIENTISTS

The Thermodynamics Division has been host in the past year to the

following scientists who have worked with NBS scientists on problems of

mutual interest.

Liebman, J.F., University or Maryland-Baltimore County, Baltimore, MD,

completed an evaluation of enthalpies of formation of amino acids,

peptides, heterocyclic and related compounds. He is an expert on techniques in estimating thermodynamimc properties of organic

compounds and on strain energies, in organic compounds.

Miller, M., University of Warsaw, Poland, Dr, Miller is working on the

crystallographic structure of proteins and DNA fragments.

Nachmann, J., Weizmann Institute of Science, Rehovot, Israel. Dr. Nachmann

is a protein crystallographer conducting neutron and x-ray

diffraction measurements of macromolecules of biological Importance

in the Biomolecular Structure Group of the Division

Nuttall, R., Former NBS employee, is an expert on solution thermodynamics

and evaluation of thermochemical data. Dr. Nuttall participated in

developing the data for electrolyte data bases and catalogs of

measurements of thermochemical data.

Rukkers, K., graduate student in the Department of Applied Physics, Twente

University of Technology, Enschede, Netherlands, spent three and a half months (Feb-May 1986) providing assistance to the large sample

flow calorimetry group improving the data acquisition and data

handling procedures.

Savage, H. , National Institute of Health, Bethesda, MD. Dr. Savage is

working on neutron diffraction of protein hormones and the structure

of bound water in biological systems.

Schumm, R.H., Former NBS employee, is an expert on the evaluation of

thermochemical data. Mr. Schumm evaluated data on sulfur compounds

relevant to flue gas desulfurization.

Shrake, A., Food and Drug Administration, Washington, D.C. Dr. Shrake is an expert in the area of thermodynamics of phase transitions in proteins

and protein ligand complexes of biological interest.

Thompson, P.T., Swathmore College, Swathmore, PA. Dr. Thompson is an expert on the interaction of organic species with water in terms of

hydrophobicity . He performed both experimental and theoretical

research during his sabbatical at NBS during calendar year 1985.

Wagman, D.D., Former NBS employee, is an expert on the evaluation of

thermodynamic data. Mr. Wagman has prepared the CODATA key values

for thermodynamics.

75
Wasik, S.P., Former NBS employee, is an expert on the evaluations of

solubility data for organic species in aqueous and mixed media. Dr,

Wasik evaluated data on the thermodynamic properties of alkanes in

aqueous media.

Weber, I., University of Maryland, College Park, MD. Dr. Weber is working

on the molecular structure of complex biomolecules using both x-ray

and neutron diffraction.

Wood, R.H., Chemistry Department, University of Delaware, Newark, DE,

worked with the staff on solution thermodynamics, theory and

experiment; electrolyte theory of weak electrolytes, speciation

calculations, molecular interactions in solution; and the

solubilities of non- electrolytes in aqueous solution as a function

of concentration and temperature.

76
NBS»n4A (REV. 2-80

U.S. DEPT. OF COMM.

BIBLIOGRAPHIC DATA

SHEET (See instructions)

1. PUBLICATION OR

REPORT NO.

NBSIR 86-3487

2. Performing Organ. Report No. 3. Publication Date

NOVEMBER 1986

4. TITLE AND SUBTITLE

Technical Activities 1986

Chemical Thermodynamics Division

5. AUTHOR(S)

6. PERFORMING ORGANIZATION (If joint or other than NBS, see instructions)

national bureau of standards

DEPARTMENT OF COMMERCE

WASHINGTON, D.C. 20234

7. Contract/Grant No.

8.

Type of Report & Period Covered

Annual Report of 1986

9.

SPONSORING ORGANIZATION NAME AND COMPLETE ADDRESS (Street, City. State, ZIP)

National Bureau of Standards

Gaithersburg, MD

10.

SUPPLEMENTARY NOTES

I I Document describes a computer program; SF-185, FIPS Software Summary, is attached.

11.

ABSTRACT (A 200-word or less factual summary of most si gn ificant information. If document includes a significant

bibliography or literature survey, mention it here)

This report summarizes the technical activities of the NBS Chemical Thermodynamics

Division during the Fiscal Year 1986. The activities of the Division include research

on: thermodynamic properties of enzyme - catalyzed reactions, DSC standards for biological systems, computer modeling of phase transitions of biomolecules, determination

of the structure of proteins and nucleic acids using x-ray and neutron diffraction,

combustion bomb calorimetry of pure substances, mass balances of chlorine during

combustion processes, high temperature heat capacity measurements, evaluation of the

thermochemistry of calcium and iron compounds, preparation of JANAF Thermochemical

Tables, and automation of Data Center procedures. A listing is provided of publications and talks given by the Division staff.

12. KEY WORDS fS/x to twelve entries; alphabetical order; capitalize only proper names; and separate key words by semicolons)

automation; biomolecular structure; bio thermodynamics; bomb calorimetry; computer

modeling; estimation; data evaluation; high temperature heat capacity; JANAF Thermochemical Tables; proteins; nucleic acids; thermochemistrv: thermodynamics

13. AVAILABILITY 14. NO. OF

1 X 1 Unlimited

1 1 For Official Distribution, Do Not Release to NTIS

PRINTED PAGES

83

1 1 Order From Superintendent of Documents, U.S. Government Printing Office, Washington, D.C.

20402. 15. Price

[X] Order From National Technical Information Service (NTIS), Springfield, VA. 22161 $11.95

USCOMM-OC 8043-P80
’ ,,= ,'Vr:^-a;j' - U-V,' ' f , J ^n l^'^'TSst 4

5\V<>*V-^A'JT<*»--:JH»Vvfv.-fl*lh^-*,*'W>'o^*4li»*|4K’.j«W^ r" ••:5<i’*’ti'}^!3’^?;rs^i«|r '-Mii ? i»

.'It,

•1l •-?- ;Lv,

t""

ii‘.D,;.|V'''V'' ^ •-/>> ^4 ifiijV>i>'r„\«.\ii: ttT!<viVu<| ^..> nvittv \^ 'f

.PiSirtjaatfrtt/aiiS^jli' . ;:>,r.4:fl»4tC‘ "-‘’^ '-^o ->^‘ :tXyX^oi

t!;.'j!.j&i'J^fin.<3-»t.‘ *3oM'V'^l<!?cK-jJf*T , ii? .s-jiiil aSji&ttifci to gjSli^i^

,iK< |>P* ’-o1- r

Jj «*»#!. ',fti0,i:3ii>cr

'

. g'M,? .:jf h r, n

.•

-3 o rrit? ^0 tsooei'fo ,«.-;<i'n'fe-:i<i<i[ia6 'os'asi-- to..

a?.'J 1*1 iA.yI.fi v» .<i«aasc X*

Xiw,i,^-<i' -‘ow,,*iu'5 SAt^A’^ lc»"' »uri^.fu^sjp',;* ficTaj" 'te^

'-,v:.^5- : >?.q , io -^1 i 4

' ...pfiVifb-*-- o.;i^ -tX;iRU ‘^0. mXS^

^

' .

' 'M^

. li''! '' '

' r‘

' '

'' "

frv>.;.vv j}<t.'..;j.ai '.int ;*f*<^»»«

'.tj.':n*i.-,.if>'':/-''' "f'VX rawir '

...V r

«;:. ’. \tP'

fl*