Hierarchial rate equations are presented for processes where events occur irreversibly and, in general, cooperatively ‘‘filling’’ the sites of a lattice (the hierarchy is infinite for an infinite lattice). We comment on the hierarchial connectivity structure and a shielding property of empty sites. Hierachy truncation techniques are developed based on these. We consider, in detail, two irreversible processes on infinite, uniform lattices with nearest neighbor cooperative effects, modeling: (i) reaction at the sites of a 1D polymer chain; and (ii) chemisorption onto the sites of a 2D square lattice. Our truncation procedure recovers previously obtained exact results for the 1D case and provides approximate results for the 2D case. These are compared in various cooperativity regimes including highly autoinhibitory rates (filling in stages) and autocatalytic rates (island formation).

1.
P. J.
Flory
,
J. Am. Chem. Soc.
61
,
1518
(
1939
).
2.
P.
Rempp
,
Pure Appl. Chem.
46
,
9
(
1976
).
3.
Reactions on Polymers, NATO Advanced Study Institute Series, edited by J. A. Moore (Reidel, Boston, 1973).
4.
I. R.
Epstein
,
Biopolymers
18
,
765
(
1979
).
5.
D. A.
McQuarrie
,
J. P.
McTague
, and
H.
Reiss
,
Biopolymers
3
,
657
(
1965
).
6.
R.
Gomer
,
Discuss. Faraday Soc.
28
,
23
(
1959
);
R.
Gomer
,
Solid State Phys.
30
,
94
(
1975
).
7.
D. A.
King
and
M. G.
Wells
,
Proc. R. Soc. London Ser. A
339
,
245
(
1974
).
8.
N. O.
Wolf
,
D. R.
Burgess
, and
D. K.
Hoffman
,
Surf. Sci.
100
,
453
(
1980
).
9.
G. A. Somorjai, Chemistry in Two Dimensions: Surfaces (Cornell University, Ithaca, 1981).
10.
J. B.
Peri
and
R. B.
Nannon
,
J. Phys. Chem.
64
,
1526
(
1960
);
J. B.
Peri
,
J. Phys. Chem.
69
,
220
(
1966
); ,
J. Phys. Chem.
J. B.
Peri
and
A. L.
Henesley
,
J. Phys. Chem.
72
,
2926
(
1968
); ,
J. Phys. Chem.
J. B.
Peri
,
J. Catalysis
41
,
227
(
1976
).
11.
E. L. Fuller, S. Ebey, and V. R. R. Uppuluri, Statistical Modeling of Adsorption Processes on Catalyst Surfaces: Preliminary Report, ORNL‐5231, Oak Ridge National Laboratory, Oak Ridge (1976).
12.
M.
Zamora
and
A.
Cordoba
,
J. Phys. Chem.
82
,
584
,
588
(
1978
); which state misleadingly that Ref. 37 shows distribution functions for irreversible processes to be of equilibrium form.
13.
G. J. M. Schmidt et al., in Solid State Photochemistry, edited by D. Ginsburg (Chemie, Weinheim, 1976), Vol. 8;
A.
Elgavi
,
B. S.
Green
, and
G. M. J.
Schmidt
,
J. Am. Chem. Soc.
45
,
2058
(
1973
).
14.
I.
Langmuir
,
J. Am. Chem. Soc.
38
,
2221
(
1916
).
15.
Z.
Nishiyama
,
M.
Oka
, and
H.
Nakagawa
,
Trans. JIM
7
,
168
(
1966
);
Z. Nishiyama, Martensitic Transformation (Academic, New York, 1978).
16.
H. Sato, in Physical Chemistry: An Advanced Treatise X. Solid State, edited by H. Eyring, D. Henderson, and W. Jost (Academic, New York, 1970).
17.
E. S.
Page
,
J. R. Stat. Soc. B
21
,
364
(
1959
);
F.
Downton
,
J. R. Stat. Soc. B
23
,
207
(
1961
);
E. R.
Cohen
and
H.
Reiss
,
J. Chem. Phys.
38
,
680
(
1963
);
B.
Widom
,
J. Chem. Phys.
44
,
3888
(
1966
); ,
J. Chem. Phys.
B.
Widom
,
58
,
4043
(
1973
); ,
J. Chem. Phys.
R. B.
McQuistan
and
D.
Lichtman
,
J. Math. Phys.
9
,
1680
(
1968
);
T. H. K.
Barron
and
E. A.
Boucher
,
Trans. Faraday Soc.
65
,
3301
(
1969
);
T. H. K.
Barron
,
R. J.
Bawden
, and
E. A.
Boucher
,
J. Chem. Soc.
70
,
651
(
1974
);
W. H.
Olson
,
J. Appl. Prob.
15
,
835
(
1978
).
18.
J. K.
Mackenzie
,
J. Chem. Phys.
37
,
723
(
1962
);
M.
Gordon
and
I. H.
Hillier
,
J. Chem. Phys.
38
,
1376
(
1983
); ,
J. Chem. Phys.
E. A.
Boucher
,
Chem. Phys. Lett.
17
,
1221
(
1972
);
E. A.
Boucher
,
J. Chem. Phys.
59
,
3848
(
1973
).
19.
J. B.
Keller
,
J. Chem. Phys.
38
,
325
(
1963
) and references therein;
D. A.
McQuarrie
,
J. P.
McTague
, and
H.
Reiss
,
Biopolymers
3
,
657
(
1965
);
E.
Klesper
,
W.
Gronski
, and
V.
Barth
,
Makromol. Chem.
150
,
223
(
1971
);
E.
Klesper
,
W.
Gronski
, and
V.
Barth
,
160
,
167
(
1972
).,
Makromol. Chem.
20.
R. L.
Dobrushin
,
Probl. Peredachi Inf.
7
,
57
(
1971
);
L. G.
Mityushin
,
Probl. Peredachi Inf.
9
,
81
(
1973
).,
Probl. Peredachi Inf.
21.
M.
Higuchi
and
R.
Senju
,
Polym. J.
3
,
370
(
1972
).
22.
N. A.
Plate
,
A. D.
Litmanovich
,
O. V.
Noah
,
A. L.
Toam
, and
N. B.
Vasilyev
,
J. Polym. Sci.
12
,
2165
(
1974
).
23.
J. J.
Gonzalez
,
Macromolecules
11
,
1074
(
1978
) and references therein;
J. J.
Gonzalez
and
K. W.
Kehr
,
Macromolecules
11
,
996
(
1978
).,
Macromolecules
24.
E. A.
Boucher
,
Trans. Faraday Soc.
69
,
1839
(
1973
);
J. J.
Gonzalez
,
P. C.
Hemmer
, and
J. S.
Ho/ye
,
Chem. Phys.
3
,
228
(
1974
).
25.
N. O. Wolf, Ph.D. thesis, Iowa State University, 1979.
26.
P. T.
Dawson
and
Y. K.
Peng
,
Surf. Sci.
33
,
565
(
1972
);
D. R.
Rossington
and
R.
Borst
,
Surf. Sci.
3
,
202
(
1965
); ,
Surf. Sci.
D. R.
Rossington
and
R. L.
Lent
,
Surf. Sci.
12
,
501
(
1968
).,
Surf. Sci.
27.
K. J.
Vette
,
T. W.
Orent
,
D. K.
Hoffman
, and
R. S.
Hansen
,
J. Chem. Phys.
60
,
4854
(
1974
).
28.
D. K.
Hoffman
,
J. Chem. Phys.
65
,
95
(
1976
);
see also
D.
Knodel
and
D. K.
Hoffman
,
J. Chem. Phys.
69
,
3438
(
1978
).,
J. Chem. Phys.
29.
J. W. Evans, Physica A (in press).
30.
J. W.
Evans
and
D. R.
Burgess
,
J. Chem. Phys.
79
,
5023
(
1983
).
31.
A. H.
Bretag
,
C. A.
Hurst
, and
D. I. B.
Kerr
,
J. Theor. Biol.
73
,
367
(
1978
) and references therein.
32.
Handbook of Mathematical Functions, edited by M. Abramowitz and I. A. Stegun (Dover, New York, 1976).
33.
R. S. Nord (private communication).
34.
D. R. Burgess, Ph.D. thesis, Iowa State University, 1982.
35.
Consider a uniform, infinite lattice of arbitrary dimension where each site has c nn sites. Suppose that filling is unaffected by the state of nn sites except when they are all occupied. Probabilities of connected groups of ⩾2 empty sites assume the same values (as functions of time) as for random filling. An expression for f0(f) may be readily obtained. If filling is blocked when all nn are occupied, then the saturation coverage is c(1+c)−1.
36.
J. W. Evans, D. R. Burgess, and D. K. Hoffman, (preprint).
This content is only available via PDF.
You do not currently have access to this content.