Catalytic
Reduction
of
CO2

 Into
Hydrogen
Using
 Microreactors
 

Malavarayan.S
 Ravishankar.M


 IInd
year
Chemical
Engineering,

 Sri
Venkateswara
College
of
Engineering,
 Sriperumbudur
 
 Postal
Address:

 No:
50,
NGO
Colony
2nd
street,
 Vadapalani,
 Chennai‐26.
 
 E­mail:
malavarayan@gmail.com
 
 Phone:
+91
9884314549
 
 




 .
The
reaction
is
carried
out
in
a
microreactor
that
 can
provide
the
necessary
experimental
conditions
viz.

The
rhodium
complex
Rh(diphos)(BPh4)
 catalyzes
the
co‐oligomerization
of
CO2
and
methyl
acetylene
to
give
 cyclic
compounds
.
Activation
of
 CO2
by
transition
metal
complexes
for
form
adducts
is
an
area
of
 investigation
[2‐8].
CO2
+
H2
have
been
used
in
the
place
of
CO
 +
H2
in
the
synthesis
of
homologous
alkenes.
The
system
 suggests
the
possibility
for
a
catalytic
cycle
for
the
fixation
of
CO2
to
 value
added
products.
of
much
importance
in
industry.
 
































This
paper
reports
the
reduction
of
CO2
to
formic
acid
 and
formaldehyde
by
the
water
soluble
K[RuIII(EDTA)Cl].
The
formic
acid
this
produced
is
converted
into
 hydrogen
by
water‐gas
shift
method
using
10%
Cu‐Al2O3
as
a
catalyst
in
 a
separate
microreactor
at
a
temperature
of
about
130
°C
to
give
 hydrogen
gas
.
therefore.Abstract:
 The
stoichiometric
reduction
of
carbon
dioxide
by
soluble
K[Ru[III]‐(EDTA‐ H)Cl].
CO2
is
used
 industrially
in
large
quantities
for
the
preparation
of
Urea
[1]
and
 inorganic
compounds
such
as
carbonates
and
bicarbonates.
The
hydrogen
thus
obtained
can
be
used
for
 various
industrial
purposes
the
most
significant
being
the
conversion
of
 hydrogen
into
Electrical
Energy
using
Fuel
Cells.
The
Energy
is
only
given
for
maintaining
the
overall
 experimental
conditions.
 
 
 Introduction:
 
 Carbon
dioxide
and
water
are
the
end
products
of
many
chemical
and
 biological
processes.
The
rates
of
formation
of
 formation
of
formic
acid
and
formaldehyde
are
of
first
order
 dependence
with
respect
to
the
catalyst
and
the
dissolved
carbon
 dioxide
concentrations.
A
stack
containing

‘n’
number
of
micro
reactors
can
 be
employed
where
‘n’
would
depend
on
the
application
of
use.2H2O
system
 under
mild
experimental
conditions
(40
‐80
°C

.
alcohols
and
amines
in
the
 presence
of
NH3

[10‐12].
the
temperature
 and
the
pressure.
The
synthesis
of
methyl
formate
by
the
reaction
of

 CO2
.2H2O
complex
at
CO2
pressure
in
the
range
of
5‐70
atm
and
 temperature
40‐80
°C
in
a
microreactor
gave
formic
acid
and
 formaldehyde
as
the
reaction
products.
The
Utilization
of
CO2
to
synthesize
value‐added
 chemicals
is.
5‐70
atm
).
H2

and
CH3OH
catalyzed
by
Ru(PPh3)Cl2
is
a
good
example
of
the
 reductive
fixation
of
CO2
[9]
.


the
experiment
was

 Conducted
with
1
mmol
of
complex
1.
later
both
the
products
tend
to
dissociate.
injector
temperature
50
°C
and
H2
 carrier
gas
with
a
flow
rate
of
30
ml
min‐1.5
m
long.
amount
of
HCHO
or
HCOOH
 formed.
 the
 rates
 of
 formation
of
HCHO
and
HCOOH
were
evaluated
in
the
interval
between
 1‐3
h.
From
the
graphs
of
time
vs.
The
concentration
of
HCHO
and
 HCOOH
present
in
the
liquid
samples
were
estimated
 spectrophotometrically
by
monitoring
the
peak
at
412
nm
using
Nash’s
 reagent
[16.
column
temperature
40
°C.5%
and
complex
 K[RuIII(EDTA‐H)Cl).
and
the
total
dissolved
CO2
concentration
 needed
to
interpret
the
kinetic
data
was
calculated.
Carbon
dioxide
gas
with
a
purity
greater
than
99.
The
bomb
was
pressurized
by
CO2
to
the
required
value
when
 the
desired
temperature
was
attained.
In
a
sample
run.2H2O
were
used
in
the
300
ml
reactor
along
with
 double
distilled
water.
The
progress
of
the
reaction
was
 monitored
by
analyzing
liquid
samples
withdrawn
at
different
intervals
 of
time
for
HCOOH
and
HCHO
contents.
a
CO2
partial
pressure
of
68.

 
 

 .
1.
The
required
solubility
data
of
 CO2
in
water
at
different
temperatures
and
pressure
were
taken
from
 the
reported
values
[18].
 Therefore.
The
column
used
 for
the
analysis
of
gases
were
2.5h.
resulting
in
a
decrease
 in
 their
 concentrations.0
atm

 And
at
80
°C.
100
mesh
with
a
TC
detector
 (150
°C).
The
yields
of
HCOOH
and
HCHO
formed
as
a
function
of

 time
is
shown
in
Fig.17].
 The
 reduction
 in
 the
 concentration
 of
 HCHO
 is
 more
 pronounced
 than
 that
 of
 HCOOH.

 Gaseous
samples
were
also
withdrawn
at
suitable
intervals
of
reaction
 time
and
analyzed
for
CO2
and
CO
content
using
a
GLC.
a
known
amount
of
complex
 1
was
dissolved
in
100
ml
of
distilled
water
and
placed
in
the
pressure
 reactor.
which
ensured
a
linear
dependence.
the
rates
of
the
formation
of
both
the
products
evaluated.
Experimental:
 
 The
carbon
dioxide
fixation
was
performed
in
a
300
ml
pressure
reactor
 by
[3].
It
is
clear
from
the
graph
that
the
concentrations

 Of
both
HCHO
and
HCOOH
increase
with
time.
The
complex
was
prepared
using
RuCl3.3H2O
and
 disodium
salt
of
EDTA
[15].
reaching
a
maximum
in

 3
‐
4
h.
 

 Results
and
Discussion:
 
 In
order
to
fix
the
conditions
for
kinetic
study.
The
decay
rate
of
HCHO
was
 evaluated
in
the
declining
portion
of
the
curve
after
3.

The yields of HCOOH (0) and HCHO (A) in CO2 reduction by K[ Rum(ED Fig
1. 1. with
a
constant
dissolved
CO2
concentration
of
3.(h) L 5 6 1 
 Fig.2H2O
 
 HCHO Kinetics
 and HCOOH were evaluated in the interval between 1 . Figures
4
&
5
show
the
plot
of
rates
of
formation
of
HCHO
and
 a first order dep respectively. Cl].9
×
10‐2
m
and
 temperature
of
80
°C
for
all
the
runs.5 . The dependence of rates of formation of HC HCOOH on the concentration of complex 1 are shown in Figs.2 X lop3 The concentration of complex 1 was varied from a
first
order
dependence
with
respect
to
complex
concentration. The experiments were pe keeping a constant complex concentration of 1 X 10e3 M. dissolved CO2 concentration.
The
dependence
of
rates
of
 formation
of
HCHO
and
HCOOH
on
concentration
of
conplex1
are
 Effect of complex concentration shown
Fig. and rates of formation of 


The
concentration
of
the
complex
1
was
varied
from
0. Both HCHO and HCOOH rates show HCOOH
vs.5
–
2
×10‐3
M
 HCHO and were evaluated.
Both
HCHO
and
HCOOH
rates
show
 0.73 X .
 ensured a linear dependence.
80
°C
and
varying
the
dissolved

CO 
concentration
from
1.98
X
 2 Effect of dissolved CO2 concentration Figures 4 and 5 show the plot of rates of formation of HC HCOOH vs.
 a constant dissolved CO2 concentration of 3. 80 “C and the dissolved CO2 concentration from 1.
dissolved
carbon
dioxide
concentration
the
experiments
 with respect to complex 1 concentration.98 X lo-* M to 7. varying
the
concentrations
of
CO2
and
rates
of
formation
of
HCHO
 and
HCOOH
were
evaluated.
 0 I 1 2 TIM:.9 X lo-* M and tempe 80 “CL! all the concentration

 for Effect
of
dissolved
CO2
runs.
The
yields
of
HCOOH
and
HCHO
in
CO2
reduction
by
K[RuIII(EDTA‐H)‐ C1]*2Hz0. were
performed
keeping
a
constant
complex
concentration
of
1
x

10‐ 3
M
. The decay rate of HCHO’was evaluat Kinetics Effect
of
complex
concentration
 The kinetic experiments on CO* reduction were conducted by the concentrations of COz.
2
and
3.3 









The
kinetic
experiments
on
CO2
reduction
were
conducted
by
 declining portion of the curve after 3.5 h.
respectively.

5 0.
Figure
6
shows
the
graph
of
‐‐In
rate
vs. From the slopes of both the straight lines. Fig. 4. respectively.5 ~10~ M COMPLEX 1 CONCENTRATION.9 X low2 M.8 dissolved CO2 concentration on HCHO Effect of kcal mol-* and 3. rate of HCHO formation.5 kcd mol-'the.x103 M Fig. Effect of dissolved CO2 concentration on the rate of HCHO formation. Figure 6 shows the graph of --In rate us.5 0. Fig. the activation1 energies evaluated for HCOOH and and HCOOH. 3. dependence with respect to catalyst and dissolved CO2 concentrations.
the
activation
energies
evaluated
for
 HCOOH
and
HCHO
are
4.73
X
10‐2
M. namely HCHO 
 . 3. l/T. Effect of complex 1 con~entratj~n on the rate of HCHO formation.9 X low2 The reduction of CO2 by complex gave two products. Mechanism The reduction of CO2 by complex 1 gave two products.
 Temperature
 The
temperature
of
the
experiments
for
reduction
of
CO2
by
complex

 1
was
varied
between
40
‐
80
°C. Fig. Fig. are 4. the activation energies evaluated for HCOOH and Fig. the products have a first-order HCHO are 4.
respectively
 
 COMPLEX j_CONCENTRATiON.8 kcal mol-* formation mol-' respectively. The rates of and 3. 
 
 
 
 COMPLEX j_CONCENTRATiON.8
kcal
mol‐1
and
3.5 kcd of both .5 ~10~ M COMPLEX 1 CONCENTRATION. Mechanism M.
From
the
 slopes
of
both
the
straight
lines. Effect of complex 1 concentration on the rate of HCOOH formation. 14 0 1. From the slopes 3. 2.10‐2
M
to
7. 3.
The
rates
of
formation
of
both
HCHO
and
 HCOOH
show
a
linear
dependence
of
CO2
concentration. 4. Effect of complex 1 con~entratj~n on the rate of HCHO formation.
with
other
conditions
constant
such
as

 Catalyst
concentration
of
1
X
10
‐3M
and
dissolved
CO2
concentration
of
 3. Effect of complex 1 concentration on the rate of HCOOH formation.x103 M 14 0 1.9
X
10‐2
M. namely HCHO of both the straight lines. l/T.5
kcal
mol‐1
. Figure 6 shows the graph of --In rate us.
l/T. 2.


The
formation
of
such
CO2
 adducts
were
reported
in
the
literature
[3
–
5].
Species
3
activates
water
 oxidatively
in
step
(2)
to
form
the
Ru(V)
species
4.Mechanism:
 
 The
reduction
of
CO2
by
complex
1
gave
two
products.
which
 reacts
with
CO2
to
form
a
CO.
Reductive
elimination
of
metalloformate
 complexes
to
formate
derivatives
such
as
methyl
formate
from
 methanol.
In
step
(5). s K LRu”‘( COz) 3 (1) (2) LRuy_-+C” ‘OR k--H 5 fast 0 (3) 1 0 LRuV + HCOOH 6 II 
 
 
 H.
the
mechanism
proposed
 for
the
reactions
is
shown
in
Scheme
1.
The
complex
1
undergoes
a
rapid
 aquation
in
presence
of
water
to
give
Ru(III)
aquo
species
2
[19].
The
insertion
of
CO2
 into
the
Ru‐H
bond
of
4
takes
place
in
step
(3)
to
form
an
η1‐formate
 species
5.
The
formation
of
ruthenium
(V)
oxo
species
6
is
 characterized
by
the
appearance
of
a
band
at
390
nm.
the
formic
acid
formed
in
step
(3)
 is
catalytically
decomposed
to
CO
and
Hz0
by
complex
2. H’ c=O + Hz0 + LRuV :: 6 (4) LYv-cN c OH- /o kl +I4 HCOOH H : OH e kz LRur”(H20) CO + Hz0 (5) .
The
rates
of
formation
of
both
the
products
have
a
first‐ order
dependence
with
respect
to
catalyst
and
dissolved
CO2
 concentrations.
The
electrons
needed
for
 the
reduction
of
CO2
to
HCOO‐
in
our
case
are
obtained
by
the
hydride
 insertion
step
(3).
Based
on
these
observations.
CO2
and
H2
had
been
reported
[9].
namely
HCHO

 and
HCOOH.) OH 4 H L&F&*) !3H k + co.
Species
6
also
 gives
v(Ru=O)
at
810
cm‐‘.
adduct
3.
The
metalloformate
complex
5
undergoes
a
rapid
 intermolecular
proto‐
nation
resulting
in
the
formation
of
formic
acid
 and
RuV‐oxo
species
6.

 
 310 LRu**~(H~O) 2 H LRu’“‘(C02) + Hz0 fast L+v(Co.

Mechanism for the stoichiometric fixation of CO2 by LFlu”‘(H20). 5.
formic
acid
 Species 3 activates water oxidatively species 4. adduct 3. Effect of dissolved CO* concentration on the rate of HCOOH formation. Effect of temperature on the rates of formation of HCOOH and HCHO. Fig. The complex 1 undergoes a rapid aquation in presence of water to give Rate
laws:
 species 2 [19]. the mechanism proposed for the reactions is 
 shown in Scheme 1. COz and Hz had been reported [9].8 2. . x10 ' M Fig. 6.0 ' / T . 111 2. 1O3 K I 3. It was confirmed by the analysis of both liquid as well as gas samples withdrawn at different time intervals that HCOOH decom- DISSOLVED CO 2 CONCENTRATION. 
The
rate
constants
for
the
water
–shift
reaction
(k3)
.1 3.51.2 
 

 Based on these observations. The metalloformate complex 5 undergoes a rapid intermolecular protonation resulting in the formation of formic acid and RuV-0x0 species 6. which reacts with CO? to form a CO. decomposition
(kCO2 into the Ru-Hin step (2) to form the Ru(V)step (3) to )

are
 
)
and
the
carbon
dioxide
reduction
to
HCHO
(k1 The insertion of 2 bond of 4 takes place in form an rjl-formate species 5.9 3.1 0 fast LRuV + HCOOH 6 II LYv-cN c OH- /o kl H. Ru(II1) aquo The formation of such COz adducts were reported in the literature [3 . 
 
 309 The rate of decomposition of formic acid catalyzed by 1 was estimated in a separate experiment. Reductive elimination of metalloformate complexes to for-mate derivatives such as methyl formate from methanol. H’ c=O + Hz0 + LRuV :: 6 (4) +I4 HCOOH H : OH e kz LRur”(H20) - CO + Hz0 (5) (6) CO + H.O k3 COz + Hz LRuV 8 6 + H\C=O H’ kq LRu”’ + HCOOH (7) Scheme 1.

solved CO2 concentration.HCOOH. i kk.] =(2)dissolved CO2 concentration.33 min-’ and=k1 evaluated at 80 “C are: 
Thus
the
above
paper
reports
on
production
of
0. 1 1 [Ru”‘(EDTA-H)(H20)IT 1 [Ru”‘(EDTA-H)(H20)lT == (4) (3) x[cozl +kk.
The
advantages
of
using
 of HCOOH [20].42
m3/s
. Thus.K 1 F2 Fl 1+ [CO21 [CO21 ‘-2 From the intercepts 
 [Ru”‘(EDTA-H)(H20)IT and =slopes of the above equations. ‘the rate constants for formic acidThe water-gas shift formation. the rate equation can be written as: Fl F2 A = kkll([Ruul(EDTA-H)(H20)]*[C02] kKIRuxl’(EDTA-H)(HaO)]r[COz] 1+ (2) 
 
 where rl = rate of formation of HCOOH. In step (7). determined independently in the absence of CO2‐ few
kilowatts
in
conventional
glassware
(1l
flask
~10
kW
m ‐ and in the presence of complex 1 at 80 “C. r2 = rate of formation of HCHO.
microreactors
can
remove
heat
much
more
efficiently
than
 vessels
and
even
critical
reactions
such
as
nitrations
can
be
 
 . The rapidly in and k. The hydrogen the
Microreactors
are
formation.03 min-’ with
4
X
10‐2
M
of
HCOOH
production
from
the
dissolved
Carbon
dioxide
 The water-gas shift reaction occurring between CO and H20 under k = 0. is 1. the rate equation can be written as: By
taking
a
300
ml
reactor
and
maintaining
at
the
optimal
experimental
 Rate laws kKIRuxl’(EDTA-H)(HaO)]r[COz] conditions
the
output
of
hydrogen
obtained
was
found
to
be
0. The value of (k3) (water-gas shift HCOOH decomposition). HCHO by K[ Ru”‘(EDTA-H)Cl] *2Hz0.
 decomposition rate constant (k.33 min-’ in
a
300
ml
reactor
under
the
temperature
of
around
40
–
70
°C
and
 the reaction conditions has a rate constant (k3 = 90. the Ru(V)-0x0 (5) is is an converted in step K=
7.03 min-’ pressure
of
about
70. K = equilibrium constant. giving CO2 HCOOH participates and Microreactors
typically
have
heat
exchange
coefficients
of
at
least
 • in The hydrogen complex 1 the “C.33
min
‐1
 species regenerating species 2. The values of k and k. 5 reacts with Hz in step (4) to give HCHO The $-carboxylate species K3and Ru(V)-0x0‐1
. k 1 1 1 and k1 evaluated at 80 “C are: (4) Results
and
Conclusions:
i kk. The formic acid ³
K ¹)).42
m3/
s
of
hydrogen
 Kkl 7. The is utilized and Hz.1
min
 ofRate laws of COz.
up
to
500
MW
m‐³
K reduction rate constant HCHO.1 min-‘) reported in our kl = 3. Thus. where rl = rate of HCOOH. = rate constant of HCHO formation.9
bars.46 M-i = = 3. [CO. and k. giving CO2 earlier studiesparticipates values of kthe water-gas rate constants for formic and Hz.occurring between muchand H20 than k3 and formaldehyde reaction respectively. The CO obtained in step (5) is rapidly converted rate
constants
are
evaluated
as

 [20].) is smaller than (k3) (water-gas shift Thus. to COz by the water-gas shift reaction 311 The $-carboxylate species 5 reacts with Hz in step (4) to give HCHO 
 and into species The CO product poses Ru(V)-0x0and HzO. obtained oxidizedspeciesrapidlyendLRuV=O 
 ofCOz by the water-gas shift reaction [20]. [Ru”‘(EDTA-H)(H20)lT = (3) Equations (1) and (2) can be rearranged in the following form to evaluFl ate the kinetic constants.) is smaller than k2 (rate constant for ‐¹
vs.


 Fl A From the kinetic observations of the reduction of CO2 to HCOOH and 1+ [CO21 
 HCHO by K[ Ru”‘(EDTA-H)Cl] *2Hz0.rapidly in the water-gas shift in the absence ofCO2 determined independently reaction. ‘-2 K = 7. are CO smaller under that
can
maintain
the
optimum
experimental
conditions
at
the
same
 and hence conditions has reduction the (k3 = 90.1 min-‘) reported in our the reaction during the CO2 a rate constantCO generated by the decomposition time
give
the
standard
CO2
mentioned
above
. k = rate constant for the formation of HCOOH. and k.52 min-‘. reduction HCHO is to HCOOH by to K1=0. are much smaller than k3 in hence during of CO2 reduction the CO generated by the decomposition and the reduction the HCOOH and HCHO. In step (7). ‘the shift reaction. Equations (1) and (2)total be rearranged in the following form to=evalu[ Ru”‘(EDTA-H)(H20)lT = can complex 1 concentration. k = rate constant for 1+ [CO21 
 the formation of formation of = rate constant of HCHO formation. the values of K.
The
proposal
is
the
usage
of
Microreactors
 earlier studies [20]. k k 0. is 1.K x[cozl 1 +kk. [CO.] disate the kinetic constants. the presence ofproduced by at 80water-gas shift reaction formic acid indecomposition of HCOOH and (k. HCHO is oxidized to HCOOH by LRuV=O reduction 
 speciesFrom the kinetic observations of the reduction of CO2 to HCOOH and regenerating species 2. by the water-gas shift reaction is utilized acid and formaldehyde produced respectively.46
M‐1CO of COz. r2 = rate of formation of HCHO.
 species 6.
a
 the 1
megawatt
per
cubic
meter
per
kelvin. the values of K. K = equilibrium constant. 6..given
as
in
the
following
precedence

 
 


K3
>>
K2
>>
K1
>>
K
>>
K4
 
 311 From
the
intercepts
and
slopes
of
the
rate
equations
given
below
the
 poses into CO and HzO.52 min-‘.46 M-i 
 From the intercepts and slopes of the above equations. the Ru(V)-0x0 species is an end product =
90.. kkll([Ruul(EDTA-H)(H20)]*[C02] [= Ru”‘(EDTA-H)(H20)lT = total complex 1 concentration. The value of k2 (rate constant for 
 ofHCOOH decomposition).


Especially
low
temperature
 chemistry
with
reaction
times
in
the
millisecond
to
second
range
 are
no
longer
stored
for
hours
until
dosing
of
reagents
is
finished
 and
the
next
reaction
step
may
be
performed.
reaction
temperatures
may
be
 much
higher
than
in
conventional
batch‐reactors.
Many
low
 temperature
reactions
as
organo‐metal
chemistry
can
be
 performed
in
microreactors
at
temperatures
of
‐10°C
rather
than
‐ 50°C
to
‐78°C
as
in
laboratory
glassware
equipment.
Thus.
 although
typical
Arrhenius
behaviour.
This
rapid
work
up
 avoids
decay
of
precious
intermediates
and
often
allows
better
 selectivities
.
This
allows
the
 subsequent
processing
of
unstable
intermediates
and
avoids
 typical
batch
workup
delays.
In
contrast.
Heating
and
cooling
a
microreactor
is
also
much
 quicker
and
operating
temperatures
can
be
as
low
as
‐100
°C.
This
may
be
an
advantage
or
disadvantage
depending
 on
the
reaction
mechanism
‐
it
is
important
to
be
aware
of
such
 different
concentration
profiles.
Thus.
microreactors
may
 allow
better
kinetic
investigations.
A
and
B
 are
mixed
nearly
instantly
and
B
won't
be
exposed
to
a
large
 excess
of
A.
As
a
 result
of
the
superior
heat
transfer.
 Continuous
operation
and
mixing
causes
a
very
different
 concentration
profile
when
compared
with
a
batch
process.
 batch
processes
too
often
perform
well
on
R&D
bench‐top
level
 but
fail
at
batch
pilot
plant
level

 Pressurisation
of
materials
within
microreactors
(and
associated
 components)
is
generally
easier
than
with
traditional
batch
 reactors.
In
a
 batch.
 Although
a
bench‐top
microreactor
can
synthesize
chemicals
only
 in
small
quantities.
 Microreactors
are
normally
operated
continuously.
reagent
A
is
filled
in
and
reagent
B
is
slowly
added.
B
 encounters
initially
a
high
excess
of
A.• • • • performed
safely
at
high
temperatures.
This
allows
reactions
to
be
increased
in
rate
by
raising
 the
temperature
beyond
the
boiling
point
of
the
solvent.
 .
is
more
easily
facilitated
in
 microreactors
and
should
be
considered
a
key
advantage.
This.
because
local
temperature
 gradients
affecting
reaction
rates
are
much
smaller
than
in
any
 batch
vessel.
scale‐up
to
industrial
volumes
is
simply
a
 process
of
multiplying
the
number
of
microchannels.
Hot
spot
temperatures
as
 well
as
the
duration
of
high
temperature
exposition
due
to
 exothermicity
decreases
remarkably.
In
a
microreactor.

15 A. H. B. 1952. p. E. New York. Ser. Mulford and W.
The
hydrogen
thus
produced
can
be
used
in
the
production
of
 as compared to HCOOH.3 e. Academic Press. Chem. the enthalpies and entropies are more Pressurisation
may
also
allow
dissolution
of
reactant
gasses
within
 negative in HCHO formation than HCOOH formation. Shukla. S. (1977) 708. Hendriksen. 6 T.. Chem. Interscience. S. 0. S. Volpin. p. Znd. Russ. Brennst-Chem. 13 P. Chem. M. Taqui Khan. Kaplan (eds. Taqui Khan. A. Abdi. I.u. G. New York. Aresta and C. B. F. Wood and H. Comprehensive Organometallic Chemistry. Othmer. 
 
 References References 1 K. R. Kolommikov. E. S. 1982. 

 20 M. 313. N. Grigoryan. Am. 287 . Kuster. Rev. 20 (1981) 1142. 4 (1965) 265. Ed. Ramachandraiah and M. Halligudi. Hailigudi and S. P. Catal. 548. Engl. J. Dalton Trans. Solubilities of Inorganic Compounds. Adu. Methods of Enzymology. Becker and M. V. 7 D. J. Russel. S. Kolommikov. 10 F. Vol. M. Am. in E. G. Wilkinson. R. J. Znorg. Mol.. Chem. E. Nash. in S. 55 (1953) 416. J. 
 . 21 M. J. 1983. Sneeden. Chem. Halligudi and S. 5 R. p. Vol. The Electricity
in
fuel
cells
as
well
in
production
of
ammonia
and
other
 negative enthalpy reflects the organic
compounds. Amjad Hussain. J. Catal. Nobile. Sot. Vol. F. Tsutsui (eds. S.. 190 (1980) 243. 90. 1975. Dev. J. J.. hence a more negative entropy. Linke. 51 (1989) 161. Taqui Khan. Chem. Sot.
 higher bond strength in HCHO and HCOOH. Organometallic Reactions. Lobeeva and M. 2 R. 74 (1952) 1969. Anderson.289. 18 A. Chem. Nageswara Rao and S. Volpin and I. A.. N. New York. Since a hydrogen the
flow
stream. Chem. A.). Taqui Khan. Diamantis and J.. Res. Znt. Chem... W.. 17 H. in G. 9 I.). Eisenberg and D. 5. Angew.. F. (Engl. 4 I. for HCHO. Aresta. T. Mol. 

 19 M. Stone and E. Eng. N. F. Moiz. 3 M. Gest. Biochem. Chem. Pergamon. 16 T. Prod. These entropies are considerably more negative than the entropies observed [21] for the conversion of CO to HCOOH and HCHO. A. 47 (1978) 334. Shukla. 225 . 12 H. Am. 25 (1986) 3023. Encyclopedia of Chemical Technology. 11 R. 99 (1977) 2391. pp. 106 (1984) 3750. Khim.. the transition state requires greater reorganisation in HCHO reaction yield. 17 (1963) 203. Wiley-Interscience. Abel (eds. W. Oxford. Transl. Kh. Seidel and W. 3.. Colowick and N.).u.). S. 8 M. New York.are +12.. Kolommikov and M. 28 (1979) 79. for HCOOH and +8. Znorg. 45 (1988) 215. J. 27 (1988) 1735. Nauk SSSR. Sot. Akad. J. Sot. B. Dubrawaski. Karn. B.283 and references therein. Herskovitz. Organometall. Ovalles.
 molecule is needed for the reduction of coordinated q’-format0 or a formyl Thus
using
stacks
of
microreactors
one
can
achieve
very
high
power
 group. Darensbourg and C. Schultz and R. Zzu. 1957. Albano and M... p. In general. 14 M. (1972) 2329. S. M. Van Nostand. 23. Catal. This reflects the higher order of rearrangements in the coordination sphere of the metal ion in CO2 insertion as compared to CO insertion. M. P.3 e.

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