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oi

.. ..-

tt

7.825 t L

Z 7.815

4155

7.410

7.405

CHLOROPHYLL A

;
i

7.400

ff---------7,100

I
c
z
w
a
Q

2n

7.090

a
7,470

, , , , , , , , , , , , ,

CHLOROPHYLL B

I2

15

18

21

24

27

30 33

36

7.080

39 4 2

TI M E ( s e c )

Figure 1. Ejection of protons from chlorophyll-quinone


systems in methanol. Right ordinate represents
results obtained in air. The upward arrows represent light
on; downward, light off. Top figure: chlorophyll a,
3.7 X
M ; with quinone, 0.03 M . Bottom figure:
chlorophyll b, 2.3 X l o + M ; with quinone, 0.03 M .

10-6 M . Proton ejection has also been observed in


the present study with the quinone systems of pheophytin, bacteriochlorophyll, and hematoporphyrin.
These studies will be reported later.
A possible explanation of the observations is presented in the following simplified scheme
CHLH h', CHLH*

(1)'

CHLH* --f CHLH'

(2)

The results presented in the present paper are not


only important in gaining insight into the mechanism
of the light-activated electron transfer of chlorophyll
systems but also lend support to the current hypothesisll
which relates the dissociation of some form of chlorophyll to the chemiosmotic12theory of photophosphorylation in photosynthesis.
(6) R. Livingston, Quart. Rev. (London), 14, 174 (1960).
(7) E. Fujimori and M. Tavla, Photochem. Photobwl., 5, 877 (1966).
(8) R. Livingston and K. E. Owens, J . Am. Chem. soc., 7 8 , 3301
(1956).
(9) G.0.Schenck, Nuturwissenschuften, 40, 205 (1953).
(10) C. 0.Ritchie and G. H. Megerle, J. Am. Chem. soc., 89, 1447
(1967).
(11) H.T. Witt, G. Doring, B. Rumberg, P. SchmidbMende, U.
Siggel, and H. H. Stiehl in "Energy Conversion by the Photosynthetic Apparatus," Publication No. 19,Biology Department, Brookhaven National Laboratory, Upton, N. Y., 1967, p 161.
(12) P. Mitchell, Nature, 191, 144 (1961).

PHOTOCHEMISTRY
SECTION
ENERGETICS
BRANCH
SPACEPHYSICS
LABORATORY
L. G. HANSCOM
FIELD
BEDFORD,
MASSACHUSETTS 01730

K E N N E T P.
H QUINLAN
EIJI FUJIMORI

RECEIVED
AUGUST14, 1967

The Intracrystalline Rearrangement of


Constitutive Water in Hydrogen Zeolite Y

CHLH'(CHLH*)

+ Q +CHL. + Q . - + H +

(3)

where CHLH* and CHLH' are the excited singlet and


triplet states of chlorophyll. The interaction of
quinone with either of the excited states of chlorophyll
as in eq 3 is well documented.6 Figure 1 also shows
that the proton ejection activities are of the same order
of magnitude whether air is present or not. This is
surprising since both quinone and oxygen are known
to compete for the excited states of chlorophyll.6
The role of the chlorophyll-oxygen
in these
light-activated reactions is uncertain. This aspect of
the problem is currently under investigation.
The ejected proton in the present system can originate
from two possible sources: (A) reaction 3 and (B) the
solvent, where CHLH. + is a cation of a weak base and
Q . - is an anion of a strong acid. Studies performed in
the aprotic solvent, dimethylformamide, show that a
proton is ejected as in reaction 3. In this study a calomel electrode, containing a saturated solution of KC1
in dimethylformamide, was used. The theoretical
behavior of this type of an electrode system has recently been shown by Ritchie and Megerle.1

Sir: The loss of constitutive or chemical water from


hydrogen zeolite Y occurs at temperatures above 500"
at
torr.'P2 We have found that this reaction occurs
in several minutes, using an inert purge gas at 650 to
750" and approximately 760 torr. The product has
poor thermal stability.
Hydrogen zeolite Y heated 2-4 hr at 700-800" in an
inert static atmosphere, where the chemical water
remains in the environs of the hydrogen zeolite, yields
a substance of unusually high thermal stability. This
material remains crystalline on heating to 1000",
whereas sodium and hydrogen zeolite Y both lose their
zeolite crystal structure at temperatures below 950".
McDaniel and Maher report the synthesis of a zeolite
Y of similar high ~ t a b i l i t y . ~They do not define the
critical requirements for its formation nor do they
account for its composition.
(1) H. A. Szymanski, D. N. Stamires, and G. R. Lynch, J. O p t . SOC.
Am., 50, 1323 (1960).

(2) J. B. Uytterhoeven, L. G. Christner, and W. K . Hall, J . Phys.


Chem., 69, 2117 (1965).
(3) C. V. McDaniel and P. K. Maher, preprint of paper presented
a t Molecular Sieve Conference, London, April 1967.

Volume 71, Number 12 November 1967

COMMUNICATIONS
TO THE EDITOR

4156

Scheme I

Si

I
I

Si

I &Si
I

4Si-+A1

H
f

+ 3H20

--.f

3 Si-0-H

H-0-Si

Si

+ Al(0H)a

Si

I1
V

Si

Si

O
3Si-O-Al

I I

&Si

iAI(OH):, + 3%-0-Al-0-Si
II

I
I

Si

Si

e
f

+ HzO

In this stable zeolite, approximately 25% of the


aluminum is present in cationic form. Clearly this
cationic aluminum is derived from tetrahedrally coordinated aluminum that was initially in the anionic
zeolite framework. About 80-9070 of this aluminum
is exchanged by sodium ion on treatment with 0.10 N
sodium hydroxide solution. The resulting sodium form
of the aluminum-deficient zeolite is also markedly more
thermally stable than the ordinary sodium zeolite Y.
The cause of this increased stability is under study.
This zeolite contains 175 (Si
Al) tetrahedra per
unit cell in the anionic framework compared with 192
universally recognized in faujasite. Obviously this
stable material is chemically different from the usual
fauj asites.
We propose the mechanism shown in Scheme I to
explain the role of chemical water and the formation
of cationic aluminum. Reaction 1 is a hydrolysis involving chemically derived water. Any technique for
keeping this water in the system during the heating
process will result in a stable product. Reaction 2 is
a neutralization involving the newly formed transient
Al(0H)I and Brgnsted acid sites that still contain
chemical water. The cationic aluminum species in

The Journal of Physical Chemistry

Al(OH)2@

I11
structure I11 may react with one or two additional
protons t o yield Al(OH)2+and A13+. Studies to be reported later show that cationic aluminum has an average charge of 1.5, indicating the presence of both Al(OH)z+ and A1(OH)2+.
Thermogravimetric studies of the stable material suggest that it contains no chemical water in its final form.
Therefore, the four hydroxyl groups in structure I1 are
probably lost as water, resulting in some type of
Si-0-Si bonding. The nature of these sites is not
presently known, but the pronounced contraction of
the unit-cell dimensions of this material, relative to
sodium and hydrogen zeolite Y, is probably related to
the formation of the aluminum-deficient sites. Water
derived from these sites and from the proposed hydroxylated aluminum cations is available for hydrolysis
of additional Brpinsted acid sites. Details of our
investigation will be reported later.
MOBILRESEARCH
AND
GEORQE
T. KERB
DEVELOPMENT
CORPORATION
CENTRAL
RESEARCH
DIVISION
LABORATORY
PRINCETON,
NEWJERSEY 08540
RECEIVED
JUNE23, 1967