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79

Thermodynamics of M u l t i - S t e p Water
Decomposition Processes

r'

James E . Funk
College of Engineering
University of Kentucky
Lexington, Kentucky 40506
Processes which c o n v e r t water i n t o hydrogen and oxygen are of i n t e r e s t
f o r many reasons, including t h e many advantages accruing t o t h e t r a n s p o r t of energy a s hydrogen. Hydrogen may be used a s a source of t h e r m a l o r e l e c t r i c a l energy, depending on whether it i s burned or used i n
an electrochemical device such as a f u e l c e l l .
Hydrogen i s a l s o a key raw material i n t h e chemical process i n d u s t r i e s
I t i s estimated t h a t by 1975 t h e t o t a l
and i n petroleum r e f i n i n g .
consumption of hydrogen i n t h e U . S . w i l l b e a t t h e r a t e of f o u r t r i l l i o n c u b i c f e e t p e r year and growing. Gaseous and l i q u i d hydrocarbons
are now t h e p r i n c i p a l r a w m a t e r i a l s f o r producing l a r g e q u a n t i t i e s of
hydrogen by means of e i t h e r c a t a l y t i c steam reforming or p a r t i a l oxid a t i o n . The p r e s s u r e f o r inexpensive and p l e n t i f u l p i p e l i n e g a s ,
a r t i f i c i a l n a t u r a l g a s , w i l l i n c r e a s e t h e demand for hydrogen even
more.
I t would c l e a r l y be i n t h e i n t e r e s t of conservation of n a t u r a l
resources t o develop an economical process t o produce hydrogen from
water.

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A comprehensive study of thermal processes t o produce hydrogen from


A three
water was performed and r e p o r t e d by General Motors ( 1 , 2 ) .
s t e p process involving e i t h e r tantalum c h l o r i d e o r bismuth c h l o r i d e
and a four s t e p process using e i t h e r mercury c h l o r i d e or vanadium
c h l o r i d e w e r e described. A g e n e r a l d i s c u s s i o n of energy requirements
f o r t h e decomposition of water was published by Funk and Reinstrom ( 3 )
and, more r e c e n t l y , a f o u r s t e p thermal process w a s described by
deBeni and Marchetti ( 4 ) . A review of t h e c u r r e n t s t a t u s of e l e c t r o l y t i c hydrogen as a f u e l has been published by Gregory, e t . a l . ( 5 ) .

Second Law L i m i t a t i o n s
I f one gram mole of water of l i q u i d water a t 25OC and 1 atm i s convert e d i n t o one gram mole of hydrogen and one h a l f gram mole of oxygen a t
25OC and 1 atm t h e gibbs f u n c t i o n f o r t h e s y s t e m i n c r e a s e s by 56.7
k c a l , t h e enthalpy i n c r e a s e s by 68.3 k c a l and t h e entropy i n c r e a s e s by
39 cal/OK.
I f t h e decomposition i s done r e v e r s i b l y a t 25OC a n d 1 atm-say i n an e l e c t r o l y s i s cell--56.7 k c a l , t h e change i n t h e gibbs funct i o n , must be supplied as u s e f u l work and 11.6 k c a l , t h e d i f f e r e n c e
between t h e enthalpy change and gibbs f u n c t i o n change, must be supp l i e d as h e a t .
The amount of u s e f u l work required may be decreased by o p e r a t i n g t h e
s i n g l e s t e p decomposition a t some higher temperature. The amount of
energy r e q u i r e d as h e a t w i l l i n c r e a s e by t h e same amount t h a t the work
required i s decreased under t h e b e s t c a s e assumptions of e q u a l specif i c h e a t s and p e r f e c t thermal r e g e n e r a t i o n of products and r e a c t a n t s .
If the process i s depicted on a temperature entropy diagram, t h e work
r e d u c t i o n i s equal t o t h e a r e a enclosed when t h e process loop i s
c l o s e d by allowing t h e c o o l e r hydrogen and oxygen t o form water

r e v e r s i b l y , s a y i n a f u e l c e l l . From t h i s viewpoint t h e process i s a


h e a t engine and i s , t h e r e f o r e , l i m i t e d i n e f f i c i e n c y t o t h e "Carnot"
e f f i c i e n c y . This second law l i m i t a t i o n has been d i s c u s s e d i n more
d e t a i l elsewhere ( 1 , 2 , 3 ) .
It i s d e s i r e a b l e , of course, t o reduce t h e amount of u s e f u l work req u i r e d t o decompose water s i n c e such work must be produced from h e a t
i n an engine of some sort. A f i g u r e of m e r i t , q,may be d e f i n e d such
that
q

bH,

(1)

Qt
AHo = 68.3 k c a l

where
.

Qt

= t o t a l amount of h e a t r e q u i r e d by p r o c e s s which a c c e p t s 1
gram mole of l i q u i d water a t 25OC and 1 atm and d e l i v e r s 1
gram mole of hydrogen and 1 / 2 gram mole of oxygen a t 25OC
and 1 atm.

L i m i t a t i o n s on 17 r e s u l t i n g from t h e f i r s t and second lawsof thermodynamics have a l r e a d y been d e r i v e d and d i s c u s s e d ( 3 ) .


The q u a n t i t y Qt comprises two t e r m s ,

Qt=

(+)+Q
I

where W = energy a s u s e f u l work r e q u i r e d


5 = e f f i c i e n c y of c o n v e r t i n g h e a t t o work
Q = thermal energy r e q u i r e d

A 1 0 0 % e f f i c i e n t e l e c t r o l y z e r o p e r a t i n g w i t h a power p l a n t w i t h a 5 of
30% would y i e l d a v a l u e f o r 17 of 34%. I f t h e e l e c t r o l y z e r had a volt a g e - e f f i c i e n c y of 6 0 % q would drop t o 2 2 % .

Multi-Step Processes
I f one supposes t h a t w a t e r i s t o be decomposed by h e a t i n g it and separ a t i n g t h e components (i.e.,a s i n g l e s t e p p r o c e s s ) t h e r a t e of reduct i o n of t h e change i n gibbs f u n c t i o n with temperature i s approximately
e q u a l t o t h e r e a c t i o n entropy change. As w i l l be shown l a t e r , t h e
t h e o r e t i c a l work of s e p a r a t i o n i s equal t o o r g r e a t e r t h a n t h e change
i n the gibbs function.
For a s i n g l e s t e p p r o c e s s t h e work requirement simply does n o t decrease
f a s t enough as t h e temperature i s i n c r e a s e d because t h e entropy change
f o r t h e r e a c t i o n i s more o r less c o n s t a n t and n o t l a r g e .
I n a multis t e p process t h e r e a c t i o n entropy change i s not f i x e d and may vary
according t o t h e r e a c t i o n .
Consider t h e i t h r e a c t i o n i n a m u l t i - s t e p process.
requirements a r e

w ( i ) = wo(i)

As(i)

[T(i)

q(i) = qo(i)

As(i)

[T(i)

The work and h e a t

To]

(3)

To]

(4)

I t h a s been assumed t h a t A s ( i ) , t h e r e a c t i o n entropy change, i s independent of temperature. The s u b s c r i p t zero r e f e r s t o c o n d i t i o n s a t t h e


r e f e r e n c e temperature, To, (assumed t o be 25OC).

IJ

81
The total work and heat requirements are obtainedby summing (3) and
(4) over the I reactions to obtain
i=I

= AG,

AS(^)

[T(i)

- To]

(5)

i=l

Another important feature becomes apparent if the process is divided


into J reactions which have positive entropy changes and L reactions
which have negative entropy changes. To minimize the required work,
the first group of reactions should be operated at some high temperature, TH, and the second group operated at To. In this case,
1

- To]

(7)

j=1
As is evident from Eqn. (-71, the required work is zero when

There is no reason why ( 8 ) cannot be satisfied along with


J

i=I

i=J

l=L

This result cannot be obtained for a single step process, in which


case the zero work requirement must be accomplished by a temperature
manipulation rather than the selection of a suitable sequence of
reactions.
Work of Separation
The theoretical work of separation, AGs, required to separate a mixture of ideal gases into its components is given by
AGs =

R T . nk
~ In Xk

(10)

is the number of moles of the kth component and xk is the


where
mole fr ction of that camponent.

Fig. 1 shows a reaction process which accomplishes the reaction

82
The amount of material e n t e r i n g t h e s e p a r a t o r depends on E , t h e f r a c t i o n a l molar conversion of R1, which i n t u r n depends on t h e standard
f r e e energy change f o r t h e reaction, AGR. Combining t h e d e f i n i t i o n of
t h e standard f r e e energy change f o r a r e a c t i n g mixture of i d e a l g a s e s
w i t h Eqn. (10) y i e l d s

A G =
~ A G ~ - R T l[ 1~I n

s1+ r2

In

s2+ --- - ( C p - C r )

I n p*]

(12)

where
and p* i s t h e o p e r a t i n g p r e s s u r e

4x1.

(12) shows t h a t t h e t h e o r e t i c a l work of s e p a r a t i o n i s g r e a t e r


than standard f r e e energy change f o r t h e r e a c t i o n .

An example of t h e t h e o r e t i c a l work of s e p a r a t i o n f o r t h e vanadium

c h l o r i d e process i s shown i n Figs. 2 and 3. Fig. 2 i s a schematic of


t h e first s t a g e i n which t h e r e is a g a s phase r e a c t i o n of c h l o r i n e
w i t h w a t e r a t 1000K a t 1 atm. Pig. 3 shows t h e t h e o r e t i c a l w o r k of
s e p a r a t i o n and it may b e noted t h a t t h e s e p a r a t i o n work i s increased
i f the mixture l e a v e s the r e a c t i o n chamber a t less than equilibrium
c o n d i t i o n s . Fig. 3 i s f o r t h e s e p a r a t i o n of a l l f o u r components and
t h e minimum work requirement is 9.2 k c a l p e r gram mole of hydrogen
produced. A similar c a l c u l a t i o n f o r t h e s e p a r a t i o n of only t h e HC1
and O2 y i e l d s a work requirement of 7.1 kcal.

The Vanadium Chloride Process


The e n t i r e vanadium c h l o r i d e process i s shown i n Fig. 4. The sums of
t h e enthalpy, entropy, and f r e e energy changes &o n o t e x a c t l y equal
t h o s e f o r w a t e r composition because of q u e s t i o n a b l e thermochemical-data.
This process w a s s t u d i e d i n c o n s i d e r a b l e d e t a i l . A p l a n t
made assuming a helium cooled n u c l e a r r e a c t o r a s t h e h e a t
Estimates w e r e made f o r pumping, h e a t r e g e n e r a t i o n , etc.
are shown i n Table 1 and, as can be s e e n , t h i s process i s
e f f i c i e n t as a w a t e r e l e c t r o l y s i s p l a n t .

l a y o u t was
source.
The r e s u l t s
not as

The o b j e c t h e r e i s n o t to d e s c r i b e an i n e f f i c i e n t process - any number


of such processes can be e a s i l y devised.
It is, rather, an attempt t o
i n d i c a t e t h a t p r o c e s s e s which may be i n i t i a l l y a t t r a c t i v e can q u i t e
quickly l o s e t h e i r a p p e a l when subjected t o sanewhat more p r a c t i c a l
c o n s i d e r a t i o n s of work of s e p a r a t i o n , thermal r e g e n e r a t i o n , pumping
F e r , etc. Such a r e s u l t is not e s p e c i a l l y s u r p r i s i n g i n v i e w of t h e
o b l e c t i v e , which, i n i t s most fundamental t e r m s , is an attempt t o conv e r t h e a t t o u s e f u l work more e f f i c i e n t l y t h a n i n a state of t h e a r t
power p l a n t .

I
/

r
r

References

1.

F i n a l Technical Report

2.

System Study of Hydrogen Generation by Thermal Energy, A l l i s o n


D i v i s i o n of General Motors, EDR 3714, v o l . 11, Supplement A, 1964.

Ammonia Production F e a s i b i l i t y S t u d y ,
A l l i s o n Division of General Motors, EDR 4200, November, 1965.

3.

Funk, J . E . , and Reinstrom, R. M . , "Energy Requirements i n t h e


Production of Hydrogen From Water", I & EC Proc. D e s . & D e v . ,
v o l . 5, N o . 3, pp 366-342, J u l y 1966.

4.

deBeni, G. and Marchetti, C . , "Hydrogen, Key t o t h e Energy Market",


Euro S p e c t r a , 9 , 46-50, June, 1970.

5.

Gregory, D. P., Ng D.Y.C.,


and Long, G . M., t o be published i n
Electrochemistry of Cleaner Environments, J . O ' M . Bockris, Ed.,
New York, Plenum P r e s s , 1971.

The

Adknowledgment
This work w a s done a t t h e A l l i s o n Division of General Motors and was
p a r t i a l l y supported by U.S. Army Engineer Reactors Group, F o r t B e l v o i r , V i r g i n i a . Permission t o p u b l i s h t h e s e r e s u l t s is g r a t e f u l l y
acknowledged.
Table 1
Vanadium Chloride Process D a t a Tabulation

Parameter

Maximum helium t e m perature


Minimum helium t e m perature
H e l i u m system pres-

Units

Systems

Remarks

2000

2000

1500

1500

37

37

67

67

sure

atm

10

Process h e a t i n p u t
T o t a l h e a t rejected

kcal

155

10

1 H e p r e s s u r e drop
equals 10 p s i i n

a l l cases

155

475

475

85

0
"

sz

m
m

a,

:
Lc

a
a,

Lc

0
d

JZ

ZI
c

.e,

-4

u)

a
.
m

2
a

m
3

c
0

ZI

..

a
L
l

c
0

86

100
Temperature = IOOOOK
Pressure = I atm

2 50
1

.L

(all components separated)

0.2

0.4

0.6

0.8

1.0

Extent of reaction -e

Fig. 3

T h e o r e t i c a l Work of S e p a r a t i o n

%7

0
(g]+Cl,(g)

Stage

+ 1/2

-2HCl(g)

O,(g)

a t 1340OF

0
+
-

112 Q&l)
77OF

Stage III

4VCt3(s)+2VCl4

( 9 ) + OVCC ( 8 ) at 1340OF

c3

Stage Ip:

2VCI4 (I)e ~VCJ,(E) tC12 (s) at 77OF


Enthalpy, entropy, and free energy tabulation
(values in kilocalories)

O r
-26.71 73.4
-46.0 48.3'
5 3 9 59.9

..
Fig. 4
9

Vanadi-

Chloride Process