富山大学水素同位体科学研究センター研究報告27 : 17‑26. 2007.

Isotope Effect on Methane Decomposition
observed between CH4 and CD4 over Zr

K. Watanabe, W. Shu* and M. Matsuyama
Hydrogell Isotope Researcll Cellter, University of Tbyama

Gofuku 3190, Toyama 930‑8555, Japan* present Amliation: ITER International Organization, nitium Plant Grotip(Received January 12, 2008: accepted March 12, 2008)
ABSTRACTThe decomposition of methane and deuter0‑methane (CD4) over Zr, Zr4Ni and Zr2Ni wasinvestigated to develop highly active materials for capturing tritiated methane inevitably
formed in tritium handling systems. None of the decomposition or absorption curves could
been described by any simple kinetic equations appearlng in the literature. They could
be described by a series reaction scheme including growth of carbonaceous deposits on thesurface. The reaction mechanisms were studied in more detail in the present study, and it
was revealed that the absorption/decomposition of methane proceeds via the steps CH4(g)ら

cH｡(a)曳cH2(a)曳C‑deposits.

The kinetic isotope effect on the decomposition/absorption of CH4 and CD4 Was also an‑alyzed for Zr in the light of ab initio caltulations uslng Small clusters including two or threeZr atoms.

1. Introduction
Ttitiated methane is one of the most important impurities in the tritium gas used in avariety of tritium handling facilities including tritium processing Systems Of thermonuclear
fusion reactors. This is because the tritium gas is contaminated by many impurity gases(including tritiated methane) generated during tritium handling and tritiated methane is one of

the most hazardousmaterialfor human safety and living environments. Accordingly extensive
studies have been done for removing tritiated methane from the contaminated tritium gas･

The most typical way so far developed is catalytic oxidation to produce tritiated water･ But
this method produces a large amount of tritiated waste water and gives rise to problems suchas its storage and/or detritiation of the waste water･

An attractive alternative way is the utilization of a kind of metallic compounds known
as Setters for vacuum technology. The present authors have developed promlSlng metallic

compounds consisting of Zr and a transition element of the group VIII, aZnong which thecompounds consisting of Zr and Ni are fbund to be most bene丘cial f♭r tritium handling回･They can easily absorb tritium not only in the elemental form butalso in the form of water,

ammoniaand gaseous hydrocarbons as well as non‑radioactive impurity species such as CO,
CO2, 02 and N2. Especially they could decompose and absorb methane that is most inactive

17

渡辺国昭･洲百･松山政夫

substance among the impurity gases. They work at relatively low temperature in comparison
with other gettering materialsl2, 3]･
In the previous paper, meth弧e (CH4) absorption curves f♭r Zr, Zr4Ni and Zr2Ni were ana‑lyzed by assdmlng Sequential removal of hydrogen atomsfrOm methaneand it was found thatthe sequential kinetic equations consisted of three elementary reactions as CH｡(g)うcH3(a)曳cH(･a)曳C‑deposits could reproduce the absorption curves of CH｡ rather well down to 0.1%of the initially loaded amount.

The present paper describes further details of kinetic analysis of the absorption curves anda model fb∫ understanding the kinetic processes of methane absorption by Zr in the light of

ab inilo calculations for samll clusters concerning the methane decomposition on Zr(1000)

surface. Discussion is also made for the kinetic isotope effect observed for CH4 and CD4
decomposition/absorption over/by Zr･

2. Experimentals
Although the experimental apparatus, procedures and results obtained with Zr and Zr‑Nialloys have been described in previous papers[1, 4, 51, a brief description of experimental
procedures is given below fわr readers convenience.

The sample materials concemed with the present paper is Zr. It was used as powder of 200
mesh (below 74 〃m). According to BET measurements using Kr, the speci丘c surface area was

0.08 m2/g. Decomposition/absorption curves of methane and deuter0‑methane (CD4) On Zr
surface was measured by constant volume method, and the absorption curves were glVen by

the pressure as a function of time, P(i) ‑ i, where 0.5 grams of powder were used. Prior to theabsorption measurements, the sample powder was heated at 423 K for 2 hoursunder vacuum
and then at 873 K for 2 hours as the standard activation procedures in the apparatus whose
residual pressure was ro山inely below 2･67 × 10‑6 pa･

The absorption curveLq Were measured by setting the imitial pressure at 13.3 Pa in the reaction
cell of 173 cc.

3. Kinetic Modelln the previous paper【6】, the absorption curves of methane over Zr and Zr‑Ni alloys wereanalyzed by accounting two dimensional potential energy surface (PES) calculated by using

the Gaussian 03 packagel7]. On account of the results of PES calculations, it was assumed
that the absorption of methane by Zr and Zr‑Ni alloys proceeds via the elementary reactionsaS

cH｡(9) +2 S生S‑cH3(a) +S‑H(a)n(CH3)n(H)S‑cH3(a) +2 S曳S‑cH(a) +2 S‑H(a)
n(CH)

18

Isotope Effect on Methane Decomposition observed between CH4 and CD4 over zr

2 S‑CH(a)曳S‑cHn(a),

(3)

n(cd)

where S denotes a vacant site fb∫ adsorption of respective species, S‑氏 (where 氏 ‑ H, CH,

CH3) adsorbed species,and n the amount of adsorbed species indicated in parentheses; kl, k2
and k3 are the respective rate constants.
In addition, it was assumed to reproduce the もailing part of absorption curves that carbona‑

ceousproducts formed via reaction (3) grows spherical‑segmentallyand its surface coveragecan be described by the term n慧2, where ned denotes the number of mols of the carbonaceous

deposits. Accordingly the kinetic process was described as 1)
IHlhu一 ー hu l川 " u‑(慧賢) ‑ klnCH4(so‑ncH3 lnSi2)2

4 5 6
3 【Hrl■川U IHr1川U(慧苧) ‑ (klnCH4 ‑ k2nCH3)(so ‑ncH3 ‑nSi2)2(警) ‑ k2nCH3(80 ‑ncH3 ‑nSi2)2 ‑ k3nbH,

where so represents the number of active sites on the surface and nx denotes the number ofmolecules of species X (X ‑ CH4, CH, or C).
These equations could reproduce well the observed absorption curves of CH4 over Zr, Zr4Ni
and Zr2Ni. However, more detailed examination of transition states in each elementary reaction
revealed that reaction (2) is not likely to occur. Instead, it is more plausible that the adsorbed
CH3(α) decomposes to produce CH2(α) and H(α). It suggests that one vacant site adjacent toCH3(α) is enough f♭r the decomposition. On account of this situation, the reaction mechanism

should be described ascH4(9)+2S曳S‑cH3(a)+S‑H(a)n(CH3)n(H)S‑cH3(a)+S曳sICH2(a)+S‑H(a)n(CH2)

2S‑CH2(a)曳sICHn(a).
n(cd)

Accordingly the kinetic equations should be revised as‑(%) ‑ klnCH4(so‑ncH3 ‑nc352)2

ヽJ ) )/ー ( (

円り H H0 1 2(三豊) ‑ [klnCH.(so ‑ ncH3 1n慧2トk2nCH3)](so ‑ ncH3 ‑ nSi2)(箸) ‑ k2nCH3(so‑ncH3 ‑n慧2) ‑k3nをH2,

where it is assumed that CH2(a) further decomposes to CH(a) and C(a) and they combine
together to fわrm carbonaceous deposits. It is also supposed that the coverage of CH2(α) is
1)Eqns.(29), (30) and (31) in the previous paperl6】 should be read as Eqs.(4), (5) and (6) in this paper. They

were mistyped.

19渡辺国昭･洲亘･松山政夫

negligible in comparison with other adsorbed species. This is the similar assumption made forCH(α) in the previous paper.

4. Results and Discussion
4.1. Analysis of Absorption Curves
Figures 1 and 2 shows the absorption curves over Zr for CH4 and CD4 , respectively,

at differemitemperatures, where the dots represent the observed values and solid lines arecalculated results by using the estimated rate constants obtained by trial‑and‑error丘tting

procedures･ The details of the fitting has been described previouslyl6]. It is seen in these丘gures that all of the absorption curves could be reproduced quite well by the revised kinetic

equations described above･ It should be noted that the absorption curves of CH4 COuld be
reproduced equally well by the preceding equations with the second order dependence for thesecond step decomposition of CH3(α), Eq･(5)【6]･

10∈uJr寸0 ‑0‑unOEV

一OuJ∈＼ゴoJoIUnOulV

o o

ュ

ュ

0

0

500

1000

1500

2 000

2500

3 000

35 0 0¶me /see

0

500

1 000

1 500

2000

¶me /seeFig. 1. Absorption curves of CH4 f♭r Zr at

350, 400, 450, 500 and 550 ℃

Fig. 2. Absorption curves or CD4 fわr Zr at 350,

400, 450, 500 and 550 ℃

Neglection of diffusion processes in the kinetic model is justfied by considerably fast diffusionof hydrogen and and slow di軌lSion of carbon in Zr; the di軌lSion constants are reported to be

10.0 x10‑3 Expl‑49.2 x 103/RTH8] and 3.5 x lOlS ExpL128 x IO3/RT][9] for hydrogen andcarbon, respectively, where the frequency factor is in cm2/scc. and the activation energy in
kJ/mol. It is demonstrated in Figs. 3 and 4 by plotting the change in the depth pro丘lesof hydrogan at 350 and carbon at 550 ℃, respectively, with time. The di軌1Sion pro丘les were

calculated for the infinte media by assuming that the initial depth profiles of hydrogen andcarbon were glVen by a step function with the unit concentration in a reglOn Of ‑a < X < a,where α was set to 100 A thickness, and the concentration is null outside of this region. The

solution of the differentail equation isgiven by clx,t] ‑ (1/2)(erfl(a ‑ I)/(2vB7)] + erfl(a +I)/(価)])[10]. In this case, the center of the media could be considered as the surface. Thenthe abscicca is the depth from the surface, which is measured in cm, and the ordinate the20Isotope Effect on Methane Decomposition observed between CH4 and CD4 over zr

0.000350.0003

UO!leJluaOuOU

uOneJlUOUuOU
0.000250.00020.00m50.00010.00∝IS

0

0.01

0.02

0.03

0. 04

0

0. 0002

0. 0004

0. 0006

0.00080. 001

Depth什om the surface /cm

Depth斤om the suTlace lcm

Fig. 3. Changeinhydrogen depth profile

Fig. 4. Change in cal･bon depth profile with

with time at 350 C

time at 550 ℃

concentraion of H or C in Figs.3 and 4. It is seen in Fig･3 that the hydrogen concentrationin the top‑most reg10n decreases to 0.0003 in 20 seconds and it is reduced to it's half in 80
seconds at 350 cc. It is also noticed that the front of the depth‑profile is extended to 0.035
cm from the surface. These features indicate that the diffusion of hydrogen, which is formedby the step‑wise decomposition of methane, is extremely fast even at the lowest temperature

adopted in the present study. Evidently hydrogen diffuses into bulk to be rapidly removed
from the surface and then the hydrogen diffusion does not take part in the kinetic cquations･The di臥lSion of carbon is, on the other hand, remarkably slow as seen in Fig.4. At thehighest temprature of the absorption measurement, 550 ℃, it takes 104 seconds for the carbon

concentration in the top‑most reglOn tO be reduced to one hundrendth of the initial value･ It isalso seen that it takes 105 seconds for the front of the diffusion profile to appear at the depth of
0.0007 cm, which is about one tenth of the diameter of Zトparticles used in the present study･All of these features clearly indicate that the diffusion of carbon into the bulk does not takeplace under the present experimental conditions and then it could be certainly excluded fromthe kinetic equations.

4.2. Temperature Dependence of t.he Rate Constants
Figure 5 shows the Arrhenius plots of therate constants, kl, Of CH4 and CD4 Obtainedfor Zr, where the abscissa is the rate con‑stant in 1/sec.mmo12 and the ordinate is thereciprocal temperature. It can be seen thatthe rate constants for CH4 and CD4 gaverather good linear straight lines･ The acti‑

0.00120.00130.00140.00150. 0016

Reciprocal Temperature /K 1

Vation energleS Were determined to be 72･O

and 79.7 kJ/mol for CH4 and CD4, reSP.eC‑

Fig. 5. Arrhenius plots of kl for CH4 andCD4 over Zr

tively. The respective frequency factors were21

渡辺国昭･洲亘･松山政夫

evaluated to be 7.4×103 and 8.0×104 fわr CH4 and CD4 [1/sec.mmo121, respectively･ The

difference in the activation energy was 7.7 kJ/mol, whereas the ratio of the frequency factors,
i,cH4/l/cD4, Was O･09･

Figures 6 and 7 compare the rate constants, k2 and k3, bet,ween CH4and CD4, Where theabscissa is in 1/see.mmol scale. It is noted that the data points of k2 and k3 for CD4 at 400C
were excluded for making Arrheniusplots, because the data points were not taken for a period

enoughlong time to determine these rate constants･ It is seen in these figures that in these cases
the data points scattered largely in comparison wit･h tJhose for kl･ Especially the scattering was
significant for k2･ This is because k2 mainly concerns with the first inflecting concave part of theabsorption curves, and k3 does the second inflection convex part accelerating the absorption in
the end of the absorption curves. It was rather di氏cult to evaluate their values in comparison

with those of kl. Nevertheless straight lines were drawn from theSC points, and the activation

L⊥

0.0012･･+･十L一.‑,一･:0.001i 0.0014

一

一

0.0015

TL十‑小1｣0.00010.0016｣‑0.00120.0013

Reciprocal Temperature /Kll

0. 00140.00150. 0016

Recipr∝al Temperature /K‑1

Fig. 6. Arrhenius plots of k2 for CH4and Fig. 7. Arrhenius plots of k3 for CH4 and
CD4

over

Zr

CD4

over

Zr

energies were evaluated as 47.1 and 99.2 kJ/mol for k2(CH4) and k2(CD4), respectively, andlO4and 137 kJ/mol for k3(CH4) and k3(CD4), reSPeCtively･ The activation energy for CH4
was smaller than that for CD4 in both of these cases. The differences in the activation energy

were 52 kJ/mol for k2 and 33 kJ/mol for k3･ These differences are unacceptably large as the
kinetic isotope effect･ In addition, it should be noted that the differences in the frequency
factor are also significantly large･ These points are discussed below in connection with the abinitio cluster calculations.

4.4. Isotope Effect examined by ab initio Calculation
The kinetic isotope effect observed for methane decomposition on Zr was examined byuseof the Gaussian‑03 packagel7]･ The ab inito calculations were carried out for small clusters
containing two or three Zr‑atoms on the Zr(1000) surface･ Then the distance between Zr‑atoms
was set to 3.2311 Å【1号Figure 8 illustrates a cluster consisting of two Zr‑atoms and a CH4

molecule that was given aS the activated complex for adsorption of CH4 molecules on the Zr
su血ce. The distance between Zr(1) and C(3) is 2.371 and that between C(3) and H(4,5,7) is

22

Isotope Effect on Methane Decomposition observed between CH4 and CD4 over zr

1.10 A that is almost equal to the bonding distance of C‑班 in a methane molecule. On theother lland, the C(3)‑H(6) distance is elongated to 1.375 A and the displacement vector f♭r

the imaginary vibration is directed toward the second Zr atom, Zr(2). Figures 9, 10 and ll

illustrate adsorbed CH3(a), activated complex for CH3(a) decompositionand product of thedecomposition, respectively.

In these cases, the cluster models consisting of three Zr atoms were adopted, because themodels consisting of two Zr atoms could not afford meaningful imaginary frequency for theactivated complex･ According to the models of adsorbed CH3(a) for three Zr atom system

shown in Fig･9, the distance between C‑Zr(2) is 2.212 A. The bonding distance of C‑H(4,5,7)

Zr
Zr

Zr

Fig･ 8･ Structure of the activated complex

Fig･ 9. Structure of adsorbed CH3(a) Obtained forfor methane decomposition obtained for aa cluster consisting of three Zr atoms

cluster consisting of two Zr atoms

in the adsorbed CH3(a) is almost the same at 1.100 A as that for adsorbed CH3(a), With
respect to the activated complex for decomposition of the adsorbed CH3(a) shown as Fig.10,

the Zr‑C distance is reduced to 2.065, whereas that of CIH(5,7) is kept almost the same at

1.100 A, but the length of the breaking bond of C‑H(6) is 1.706 A, where the displacement

vector of imaginary vibration is directed toward Zr(1),As for the reaction product seen in
Fig.ll, the bonding lengths of Zr(2)‑C and Zr(2)‑H(8) are 2.265 and 1.988 A, respectively.
The activation energies for CH4(9) decomposition/adsorptionand for CH3(a) decomposi‑tion/adsorption to CH2(α) are evaluated to be 199.7 and 95.3 kJ/mol, respectively, that were

calculated from the energies Of bottoms of the potential wells; that is, the classical energy dif‑ference･ These values are too large in comparison with those obtained from the experimental
data･ As mentioned in the previous paper【6], these large discrepancies should be ascribed tothe oveトSimpli丘cation of the cluster models. Nevertheless the simpli鮎d cluster models could

give SOme insight into the isotope effect on kl, k2 and k3 for the decomposition over Zr surface.
According to the calculation, the difference in the activation energy for kl between CD4 andCH4 Was evaluated to be 4･8 kJ/mol.

23

渡辺国昭･洲宣･松山政夫

Fig･ 10･ Structure of activated complex for Fig･ 11･ Product of the decomposition of

the decomposition of CH3(a) obtained for CH3(a) for Zr3‑cluster
Zr3‑cluster modelThis value agrees rather well to the value of 7･7 kJ/mol obtained from the fitting of the exper‑

imental data･ With respect to the frequency fact,or, tJhe frequency ratio of kol (CH4)/kol (CD4)can be estimated from the imaglnary frequency ratios as the hightemperature limit fromi/(CH4)/l/*(CD4) [12]. The observed ratio of about 0.1 is far smaller than the value of 1.37 cal‑culated from I/*(CH4)/l/*(CD4). But it should be accounted that the determination of the fre‑quency factor from Arrhenius plots is a troublesome problem, especially in the case that only alimited numbers of experimental data is available as in the present study. This is demonstrated

in Fig･S by the gray thick line which was drawn by assuming kol(CD4) ‑ kol(CH4)/1.37.

With respect to k3, it is expected that there appears no noticeable isotope effect because thisstep is considered to correspond to the accumulation of adsorbed species as CH2(α), CH(α)

and/or C(a) to form carbonaceous deposits on the surface. Accordingly Fig.7 should be readas the plots for k3(CH4) and k3(CD4) agrees each other. The gray thick line in Fig.7 shows
the least square五七fbr the data points of CH4 and CD4, Which gave the activation energy of

124kJ/mol.

Asfor k2, allnOSt tile Same consideration could be valid for the difference in the activationenergyand the rat･io of freqllenCy factJOrS aS the consideration for the isotope effect on kl･Namely, the difference in the activation energy was evaluated from the ab initio calculation

as 3･69 kJ/mol and the ratio of the frequency factors wasgiven as u*(CH3)/U*(CD3) ‑ 1.37.
From this viewpoint, the results shown in Fig･6 are not physically meaningfdl. This is largely
due to the difBculty for determinlng precise values from the limited number of absorption

curves with enough accuracy･ More data with higher accuracy are required to obtain reliable
k2･ Concerning this point, Zr2N showed much more plausible isotope effects and the analysis
in combination with ab initio calculations will be presented in the next paper･

5. Conclusions
Absorption curves of CH4 and CD4 fb∫ Zr were analyzed by use of a series of kinetic equations

24

isotope Effect on Methane Decomposition observed between CH4 and CD4 Over zr

and the results of kinetic analysis were further inspected by taking account of ab inito calcula‑tions for small clusters consisting of two or three Zr atomsand methane by using GaussianO3
package.

It was found that the revised kinetic model accounting the sequential removal of hydrogenatoms as cH｡(9)曳cH3(a)うcH2曳carbonaceous deposites could reproduce well theabsorption curves of CH4 and CD4. Disappearance of the di瓜1Sion process in the kinetic

equations was justified by extremely fast diffusion of hydrogen and remarkably slow diffusionof carbon into the bulk of Zr.

The kinetic isotope effects were measured from the analyses of absorption curves. The
differences in the activation energies were evaluated to be △Ek.(CD4) ‑ △Ekl(CH4) ‑ 717

kJ･mol･, whereas unacceptalbly large difference was obtained for Ek2 (CD4) ‑ AEk, (CH4) I As
for k3, it was concluded that no appreciable isotope effect appeared.

With respect to the isotope effect on kl, the ab inito calculations could provide details ofreaction mechanisms such as the structures of the adsorbed species and activated complex｣tgave the differences in the activation energies for kl between CD4 and CH4 tO be 4･78 kJ/mol･and the ratio of frequency factors, U * (CH4)/l/ * (CH4), tO be 1.37. This difference in theactivation energy was quite close to that obtained from the experimental data and it was also

true for the ratio of frequency factors. No appreciable isotope effect on k3 Was rationalized by
the reactions among decomposition products such as CQ2(α), CQ(α) and/or C(α) (Q‑H or

D), On the other hand, the unacceptalble large isotope effect on k2 Was ascribed to insuncientaccul･aCy Of the first inflecting concave part in absorpt.ion curves.

Refbrencesll] K. Watanabe, W. M. Shu, M. Motohashi, and M. Matsuyama, Fusion Engn. Design,
39/40 (1998) 1055 ‑1060[2] L. C. Emerson, R. ∫. Knize, J. L. Cecchi, and 0, Au｡iell｡, J. Vac. Sci. Technol., A4(1986) 297‑299[3] L. C. Emerson, R. 3. Knize, and I. L. Cecchi, J. Vac. Sci. Technol., A5 (1987) 258'4‑2586[4] W. M. Shu, M. Matsuyama, and K. Watanabe, Ann. Kept. HRC., Toyama Univ., 16(1996) 59‑68[5] M. Matsuyama, E. Motohashi, W. M. Shu, and K.lwatanabe, Ann. Rept. HRC., Toyama
Univ･, 17 (1997) 73‑84[6] K･ Watanabe, W･ Shu, and M. Matsuyama, Ann. Repi. Hydrogen Isot. Res. Centr., 26(2006) 1‑1225渡辺国昭･洲貞･松山政夫[7】 M･ J･ Frisch, G. W.Trucks, H･ B･ Schlegel, G･ E･ Scuseria, M. A･ Robband J･ R･ Cheese‑manand ∫. A. Montgomeryand Jr.and T. Vrevenand K. N. Kudinand ∫. C. Burantand

J. M. Millamand S. S. Iyengarand I. Tomasiand V. Baroneand B. Mennucciand M. Cos‑
siand G. Scalmaniand N. Regaand G. A. Peterssonand H. NakatSujiand M. Hadaand M.
Eharaand K. Toyotaand R. Fukudaand J･ Hasegawaand M. Ishidaand T･ Nakajimaand Y･
Hondaand 0. Kitaoand H. Nakaiand M. Kleneand X. Liand J. E. Knoxand H. P. Hratchi‑
anand J. B. Crossand C. Adamoand J. Jaramilloand 氏. Gompertsand 氏. E. Stratmannand
O. Yazyevand A. J. Austinand 氏. Cammiand C. Pomelliand ∫. W. Ochterskiand P. Y.
Ayalaand K. Morokumaand G. A. Vothand P. Salvadorand ∫. ∫. Dannenbergand V. G.

Zakrzewskiand S. Dapprichand A. D. Danielsand M. C. Strainand 0. Farkasand D. K.

Malickand A. D. Rabuckand K. Raghavachariand J. B. Foresmanand J. V. Ortizand Q.
Cuiand A. G. Babouland S. Cliffordand I. Cioslowskiand B. B. Stefanovand G. Liuand

A. Liashenkoand P. Piskorzand I. Komaromiand R. L. Martinand D. J. Foxand T. Kei‑thand M. A. Al‑Lahamand C. Y. Pengand A. Nanayakkaraand M. Challacombeand P.

M･ W･ Gilland B. Johnsonand W. Chenand M. W, Wongand C. Gonzalezand, and J･ A･Popleand, GaussianOS, RevisionB･ 03, Gaussian lnc.and Pittsburgh, 2003
[8】 Y. Fukai, K. Tanaka and H. Uchida, Suiso to Kinzoku (in Japanese), p.115, Uchida

Rokakuho Publishing Co., Tokyo, 1998

[91 The Japan Institute of Metals, Metal Databook (End Ed.) (in Japanese), p.29, Muruzen,
Tbkyo, 1984

[10] H. S. Carslaw and J. G. Jeager. Conduction ofHeai in Sollids (End Ed.), p.54, Clarendon
Press, Oxford, 1959.

[11] R. Kiriyama and H. Kiriyama, Kohzoh Muki Kagaku I, p.59, Kyoritsu Shuppan (inJapanese), Tbkyo, 1970

[12】 L. Melander, Isotope EHects on Reaction lhtes, p.44, Roland Press, New York, 196026