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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.
t
\
i
\
'
1
4
1
\\
t
\,
I
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
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.
Qt=
(+)+Q
I
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)
To]
(3)
To]
(4)
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
- To]
(7)
j=1
As is evident from Eqn. (-71, the required work is zero when
i=I
i=J
l=L
R T . nk
~ In Xk
(10)
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.
l a y o u t was
source.
The r e s u l t s
not as
I
/
r
r
References
1.
F i n a l Technical Report
2.
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.
4.
5.
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
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
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:
O r
-26.71 73.4
-46.0 48.3'
5 3 9 59.9
..
Fig. 4
9
Vanadi-
Chloride Process