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Chapter 5

Exercise 1:
part a)
The full BET equation is as follows:
 c −1 P
P
1

=
+ 
Vads ( Po − P) cVm  cVm  Po

(1)

After dividing both the numerator and denominator of the left hand side of equation (1)
by Po,
P

Po
Vads (1 − P

Po

)

=

 c −1 P
1

+ 
cVm  cVm  Po
P

By plotting

Po

P
Vads (1 − )
Po

vs P

Po

(2)

for sample 1, the following can be concluded (only the

following data points were used in these calculations 0.05 ≤ P

Po

≤ 0.3 ):

c −1
= 0.035 g cm-3
cVm
1
The regressed y-intercept of the resulting line =
= 9.15x10-5 g cm-3
cVm
2
R value of the fitted line = 0.99
The regressed slope of the resulting line =

Therefore c = 386.4 and Vm = 28.3 cm3 g-1
The one-point BET equation is as follows:
 1 P
P
=  
Vads ( Po − P)  Vm  Po

(3)

where we assume that c>>1.
Choose one point to calculate Vm. Choose P/Po = 0.3.
5.1

At P/Po = 0.3, Vads = 39.1 cm3 g-1.
Therefore Vm= V(1-P/Po) = (39.1cm3 g-1)(0.7) = 27.4 cm3 g-1.
Note that assuming c >>1 was a good assumption, as seen from the calculations done
using the full BET equation.
Now we need to calculate the surface area, Sg, for each solution.
The surface area is related to the number of molecules adsorbed in a monolayer, N, in the
following way.
S g = Nα

(4)

where α is the cross-sectional area of the adsorbing gas (dinitrogen in this case).
Vm N o
where No is Avagadro’s number and V
V
is the volume of gas at STP (1 atm and 273 K) per mol, 22400 cm3 mol-1.
N = # molecules adsorbed per monolayer =

For dinitrogen, α = 0.162 nm2.
For the full BET equation
2

molecules
 1m 
)(0.162) 9

mol
 10 nm  = 123 m2g-1.
22400 cm 3 mol −1

28.3 cm 3g −1 (6.02 x10 23
Sg =

Similarly for the one-point BET equation,
Sg = 119 m2g-1.
These values are essentially the same (3% difference).
part b)
Repeat the same analysis as in part a) except on Sample 2.
Full BET equation:
c = 22.4
Vm = 0.689 cm3g-1.
5.2

In this case the particle diameter is 1.7 m2 g-1.3 .34 = 0. Exercise 2: Note that: # moles H chemisorbed irreversibly (strong sites) = #moles H chemisorbed in Run 1.# moles H chemisorbed in Run 2 H First. The surface areas for the full BET equation and the one-point equation are 3. For the one-point equation: Vm = V(1-P/Po) = (0. the two methods do not give the same answer (10% difference).Note that this sample has a smaller BET constant than sample 1 (c is not much greater than 1 here).93 − 0.00 m2 g-1 and 2.69 nm.89cm3 g-1)(1-0. plot H/Pt vs P for each run.3) = 0. find the y-intercepts   Pt Dispersion= H/Pt irreversibly adsorbed = H Pt − P = 0 . P =0  = 0. Run 2 The average particle size is estimated using the following relationship.59 P = 0 . assuming that the particles are spherical: Particle diameter (nm)=1/dispersion. respectively. Peloso is CH3CH2OH = CH3CHO + H2 (Et) (Ad) (DH) (1) 5. Run1 H Pt   . Due to the small BET constant.623 cm3g-1. Exercise 3: The reaction investigated by A.

so surface sites are involved in the RDS. so the adsorption and desorption of DH is equilibrated (it is not dissociative adsorption).4 . K DH = [ Et ][∗] [ Ad ][∗] [ DH ][∗] (3) From the RDS. 2) The denominator is raised to the 2nd power. r= k1[ Et ∗][∗] − k −1[ Ad ∗][ DH ∗] [∗]0 (4) The site balance is [∗]o = [∗] + [ Et ∗] + [ Ad ∗] + [ DH ∗] (5) After substituting equation (3) into equation (5) 5. K Et = [ Et ∗] [ Ad ∗] [ DH ∗] . K Ad = .The proposed mechanism is: r = k [PEt − ( PAd PDH ) / K e ] (2) [1 + K Et PEt + K Ad PAd ]2 To formulate a mechanism the following clues can be gained from inspection of the proposed expression: 1) PDH is raised to the 1st power. The following mechanism is proposed: 1 Et + * 2 Et* + * 3 Ad* DH* Et* Ad* + DH* Ad + * DH + * The following analysis is used to derive the expression in equation (2).

Therefore. however a different catalyst is used. Since DO is raised to the ½ power.5 . In addition. the assumption that KDH[DH]<<1 is needed in order to arrive at the proposed rate expression. Exercise 4: This is the same reaction as Exercise 3. 5.[∗]o = 1 + K Et [ Et ] + K Ad [ Ad ] + K DH [ DH ] [∗] (6) After substituting equation (6) into equation (4). the RDS is proposed to be the following step: IP*1 + O∗2 At + W∗1 + ∗2 (3) where *1 and *2 represent two different types of active sites. DO adsorption/desorption is dissociative. the proposed rate expression can be derived. with the assistance of equation (3). there must be two types of surface sites. Since there are two terms in the denominator. KDHPDH is not << 1. Note that the constants are all lumped into k and Ke. The proposed rate expression with the new catalyst is as follows: r= k [PEt − ( PAd PDH ) / K e ] (1) [1 + K Et PEt + K Ad PAd + K DH PDH ]2 The same reaction mechanism as in Exercise 3 is proposed here. Exercise 5: The overall reaction is IP + DO = At + W (1) The proposed rate expression is of the form: 1 k[ IP][ DO] 2 r= 1 (1 + K1[ IP] + K 2 [W ])1 + K 3 [ DO] 2    (2) We shall assume that At cannot adsorb on the surface of the catalyst and that the rate of surface reaction between adsorbed IP and adsorbed oxygen is the rate determining step. The only difference between the rate expression in Exercise 3 and in Exercise 4 is that in Exercise 4.

[∗1 ] = [∗1 ]o (1 + K1[ IP] + K 3 [W ]) (9) After substituting equation (5) into equation (7). Since the surface reaction step is the RDS. [ IP ∗1 ] [O ∗ 2 ] 2 [W ∗1 ] K1 = . K3 = (5) 2 [ IP][∗1 ] [W ][∗1 ] [∗ 2 ] [ DO] The site balance for site type 1 is [∗1 ]o = [∗1 ] + [ IP ∗1 ] + [W ∗1 ] (6) while the site balance for site type 2 is [∗ 2 ]o = [∗ 2 ] + [O ∗ 2 ] (7) After substituting equation (5) into equation (6).6 . K2 = . all other steps must be equilibrated. Therefore. the site balance on site type 2 becomes 5.DO + 2∗2 2O∗2 Therefore a reaction mechanism that is consistent with the rate expression is the following: IP + ∗1 IP∗1 DO + 2∗2 IP*1 +O∗2 W∗1 2O∗2 (4) At + W∗1 + ∗2 W + ∗1 The following analysis is used to derive the rate expression from the proposed mechanism. the site balance on site type 1 becomes [∗1 ]o = [∗1 ] + K 1 [ IP][∗1 ] + K 3 [W ][∗1 ] (8) Therefore.

7 . therefore.[∗ 2 ]o = [∗ 2 ] + K 21 / 2 [∗ 2 ][ DO]1 / 2 (10) Therefore. (9) and (11) into equation (12). The following mechanism is suggested to explain the functional form of the rate expression given in equation (2). 5. ( ) k K1[ IP][∗1 ]o K 21 / 2 [∗2 ]o [ DO]1 / 2 r= (1 + K1[ IP] + K 3 [W ]) 1 + K 21 / 2 [ DO]1/ 2 ( (13) ) The rate expression in equation (2) is obtained by grouping all of the constants. Exercise 6: The overall reaction that is being studied here is the following: CO + Cl2 = COCl2 (1) The proposed rate expression for this reaction is the following: r= kPCO PCl2 [1 + K P 1 Cl2 + K 2 PCOCl2 (2) ] 2 The exponent in the denominator suggests that there are two adsorbed species in the RDS. [∗ 2 ] = [∗ 2 ]o 1 + K 21 / 2 [ DO]1 / 2 (11) The rate of the reaction is the rate of the RDS. The lack of a K3PCO term in the denominator suggests that CO does not adsorb strongly on the surface. r = k[ IP ∗1 ][O ∗2 ] (12) After substituting equations (5).

K2 = and K 3 = [CO ][∗] [Cl 2 ][∗] [COCl 2 ][∗] (5) The site balance for this system is [∗]o = [∗] + [CO∗] + [Cl 2 ∗] + [COCl 2 ∗] (6) After substituting equation (5) into equation (6). [∗] = [∗]o 1 + K1[CO] + K 2 [Cl2 ] + K 3 [COCl2 ] (7) Substituting equation (7) into equation (4). in order to arrive at the rate equation in equation (2) we must assume that K1[CO]<<1.8 . 5.CO + ∗ Cl2 + ∗ CO∗ Cl2∗ CO∗ + Cl2∗ COCl2∗ (3) COCl2∗ + ∗ COCl2 + ∗ The rate of the RDS is r= k[CO∗][Cl 2 ∗] [∗]o (4) The following equilibrium relationships are valid since the surface reaction step is the RDS: K1 = [Cl 2 ∗] [COCl 2 ∗] [CO∗] . r= kK1[CO ][∗]o K 2 [Cl 2 ] (8) (1 + K1[CO] + K 2 [Cl 2 ] + K 3 [COCl 2 ])2 Again.

9 .Exercise 7: The proposed reaction rate has the form: r= kK A PA (1 + K A PA + K B PB )2 (1) If a large quantity of inerts readily adsorb on the catalyst surface. Exercise 8: The following reaction is studied over a zirconium oxide-silica gel catalyst: C2H4 + HCl = C2H5Cl (4) Step 1: Assume a plausible reaction mechanism. C2H4 + * HCl + * C2H4* HCl* C2H4* + HCl* C2H5Cl* + * C2H5Cl* C2H5Cl + * CH4 + * CH4* (5) 5. KIPI is large compared to KAPA and KBPB and 1. The reaction rate is as follows: r= kK A PA (1 + K A PA + K B PB + K I PI )2 (2) It can be simplified to r= kK A PA K I2 PI2 (3) The reaction order with respect to A is 1 with a large quantity of inerts that adsorb on the catalyst surface.

equation (4).10 .Step 2: Derive a rate expression for this mechanism. Ke = [C 2 H 5 Cl ] = 35 [C 2 H 4 ][ HCl ] (11) After substituting equation (11) into equation (10) and rearranging [C H Cl ]  k  [C 2 H 4 ][ HCl ] − 2 5 K e   r= (1 + K1[C2 H 4 ] + K 2 [ HCl ] + K 4 [C2 H 5Cl ] + K 3 [CH 4 ])2 5. The equilibrium relationships are as follows: K1 = [C 2 H 4 ∗] [CH 4 ∗] [ HCl ∗] . K2 = . K3 = [C 2 H 4 ][∗] [ HCl ][∗] [CH 4][∗] (6) [C 2 H 5 Cl ∗] and K 4 = [C 2 H 5 Cl ][∗] The rate of reaction is that of the RDS: r= k1[C 2 H 4 ∗][ HCl ∗] − k −1[C 2 H 5Cl ∗][∗] [∗]o (7) The site balance is [∗]o = [∗] + [C 2 H 4 ∗] + [ HCl ∗] + [C 2 H 5 Cl ∗] + [CH 4 ∗] (8) After substituting equation (6) into the site balance: [∗] = [∗]o 1 + K 1 [C 2 H 4 ] + K 2 [ HCl ] + K 3 [CH 4 ] + K 4 [C 2 H 5 Cl ] (9) The rate expression in terms of only the reactants and products is: r= k1 K1[C 2 H 4 ][∗]o [ HCl ]K 2 − k −1 K 4 [C 2 H 5 Cl ][∗]o (1 + K1[C 2 H 4 ] + K 2 [ HCl ] + K 3 [CH 4 ] + K 4 [C 2 H 5Cl ])2 (10) From the overall equation.

We obtained the following parameters: k = 3.00029 0.11 . Use nonlinear regression to fit the data to this form.00025 0.00027 0. The mechanism is as follows: C2H4 + * C2H4* + HCl C2H4* C2H5Cl* C2H5Cl* C2H5Cl + * CH4 + * CH4* (12) The rate is then the rate of the RDS. Each program that is used to solve for the best fit parameters will give a slightly different answer depending on initial values.95 K3 = 1.00023 0.00021 0.where k is a grouping of constants.00019 0.14 K2 = 32.00023 0.00021 0. Calculated Rate 0.98 K4 = 32.00019 0.00025 0.86 K1 = 25. namely that of Rideal-Eley. 5.00027 0.00029 Observed Rate Now assume a different mechanism.19 The following graph shows that how these parameters represent the data.

r = k 2 [C 2 H 4 ∗][ HCl ] − k −2 [C 2 H 5Cl ∗] (13) The other three steps are assumed to be quasi-equilibrated.12 . the Rideal-Eley mechanism does not fit the data. Since this is unreasonable. r = k1[ N 2 ][∗] − k −1[ N 2 ∗] (3) The equilibrium expression is 5. the rate is given by the following expression: [C H Cl ]  k  [C 2 H 4 ][ HCl ] − 2 5 K e   r= (1 + K1[C2 H 4 ] + K 4 [C2 H 5Cl ] + K 3 [CH 4 ]) (16) However. Exercise 9: part a) The proposed mechanism is as follows: N2 + ∗ N2∗ + 3H2 N2∗ (1) 2NH3 + ∗ (2) The rate of reaction is therefore. negative numbers are found for some of the constants. and the equilibrium expressions are the following: K1[C 2 H 4 ][∗] = [C 2 H 4 ∗] K 3 [C 2 H 5 Cl ][∗] = [C 2 H 5 Cl ∗] (14) K 4 [CH 4 ][∗] = [CH 4 ∗] The site balance is the following: [∗]o = [∗] + [C 2 H 4 ∗] + [C 2 H 5 Cl ∗] + [CH 4 ∗] (15) After substituting equations (14) and (15) into equation (13). after fitting this expression to the data.

7 is k1[∗]o [ N 2 ] − k −1 K 22 [∗]o r=   [ NH 3 ]   1 + K 2  3 / 2   [ H 2 ]    [ NH 3 ] if K 2  3/ 2  [H 2 ] r= [ NH 3 ]2 [ H 2 ]3   >> 1 or  k1[∗]o [ N 2 ]  [ NH 3 ]   K 2  3/ 2   [H 2 ]  2 (8) 2  [N ∗]    >> 1  [∗]  − k −1[∗]o (9) 5.13 . [∗] = [∗]o [ NH 3 ] 2 1+ [ H 2 ]3 K 2 (6) Substituting equations (5) and (6) into equation (3) results in the rate expression for the reversible formation of ammonia with associative adsorption of dinitrogen.3.[ NH 3 ] 2 [∗] K2 = [ H 2 ]3 [ N 2 ∗] (4) The site balance for this reaction mechanism is [∗]o = [∗] + [ N 2 ∗] (5) After substituting equation (4) into the site balance.7 from the rate expression in part a) from experimental data. Equation 5. r= k1[ N 2 ][∗]o k −1[ NH 3 ]2 [∗]o − [ NH 3 ]2 [ NH 3 ]2  3 1+   K 2 [ H 2 ] 1 + 3 [ H 2 ]3 K 2 [ ] H K 2 2   (7) part b) It is not possible to distinguish equation 5.3.

the site balance is reduced to [∗]o = [∗] + [ N 2 O∗] + [CO∗] (4) The equilibrium relationships are as follows: 5.[ NH 3 ] 2 [ N 2 ∗] >>1 or >>1 From part a) if 3 [∗] [H 2 ] K 2 r= k1[ N 2 ][∗]o − k −1[∗]o [ NH 3 ]2 [ H 2 ]3 K 2 (10) Since equation (10) and equation (9) are identical it is probably not possible to distinguish between the two rate expressions experimentally unless an extremely wide range of accurate data is used. if the surface coverage of oxygen is assumed to be very small. Where the overall reaction is N2O + CO ⇒ N2 + CO2 (2) part a) The site balance for this mechanism is [∗]o = [∗] + [ N 2 O∗] + [CO∗] + [O∗] (3) However.14 . Exercise 10: The proposed mechanism is: N2O + ∗ N2O∗ CO + ∗ CO∗ + O∗ N2O∗ N2 + O∗ (1) CO∗ CO2 + 2* The adsorption of N2O and CO on the surface is equilibrated.

The rate expression is as follows: r= k 2 K1[∗]o [ N 2 O] 1 + K1[ N 2 O] + K 3 [CO ] (8) In addition.K1 = [ N 2 O∗] [CO∗] and K 3 = [CO ][∗] [∗][ N 2 O] (5) After substituting equation (5) into the site balance and rearranging [∗] = [∗]o 1 + K1[ N 2 O] + K 3 [CO ] (6) The rate of reaction is either the rate of N2O reaction on the surface or the rate of CO2 formation.15 . part b) First. r = k 2 [ N 2 O∗] = k 4 [CO∗][O∗] (7) After substituting the site balance and the equilibrium relationships into equation (7). linearize the rate expression in equation (8) from part a). the rate expression is then determined. PN 2O r Plot Plot = 1 K 2 PN 2O K 3 PCO + + K1 K1 K1 PN 2O r PN 2O r (1) vs PN 2O at constant PCO to get slope = vs PCO at constant PN 2O to get slope = K2 1 K 3 PCO and the intercept = + K1 K1 K1 K3 1 K 2 PN 2 O and the intercept = + K1 K1 K1 The results of the regression analysis are shown below: 5. let k 2 K1[∗]o = K 2 .

0 0 0 20 40 60 80 P CO There are now four equations to solve with three unknowns. Therefore.9 500 0 0 20 40 60 80 P N2O Linear Regression (Holding P N2O Constant) 5000 PN2O /r 4000 3000 2000 y = 45.6 1000 2 R = 0.007 s torr-1 K2 = 0.025 torr-1 5.320 torr-1 part c) The results of the non-linear regression using the rate expression in part a) and the data in part b) yielded the following results.16 . K1 = 0.3x + 460. K1 = 0.Linear Regression (Holding Pco Constant) 2500 PN2O /r 2000 1500 y = 8.069 torr-1 K3 = 0.7x + 1486. The average of the 4 cases was taken here.004 s torr-1 K2 = 0.4 1000 2 R = 1. there are four different ways to solve the set of overdetermined equations.

The answers in this case are within a factor of 3 of each other. the steady state approximation is used.17 .168 torr-1 The answers in parts b) and c) will be different because two different methods were used.K3 = 0. r = r1 = r2 = k1[ H 2 O][∗] − k −1[ H 2 ][O∗] = k 2 [CO ][O∗] − k −2 [CO2 ][∗] (2) Use equation (2) to solve for [O∗] [O∗] = k1 [ H 2 O][∗] + k − 2 [CO2 ][∗] k 2 [CO ] + k −1 [ H 2 ] (3) The site balance for this system is the following: [∗]o = [∗] + [O∗] (4) After substituting equation (3) into the site balance and rearranging 5. The coverage of CO on the surface must be larger than the coverage of N2O on the surface. Exercise 11: The proposed mechanism is the following: H2O + ∗ V H2 + O∗ (1) CO + O∗ V CO2 + ∗ Since we cannot assume that either step is the RDS. part d) Since K3 is large compared to K1 and K2 where K1 = [ N 2 O∗] [CO∗] and K 3 = [∗][ N 2 O] [CO ][∗] and K2 from the regression analysis was equal to the equilibrium constant K1.

r= k1[ H 2 O][∗]o (k 2 [CO ] + k −1[ H 2 ]) − k −1[ H 2 ][∗]o (k1[ H 2 O] + k −2 [CO2 ]) k 2 [CO ] + k −1[ H 2 ] + k1[ H 2 O] + k −2 [CO2 ] part b) The Langmuir-Hinshelwood type mechanism for the WGS reaction is: CO + ∗ H2O + 3∗ CO∗ + O∗ 2H∗ CO∗ 2H∗ + O∗ (1) CO2 + 2* H2 + 2∗ The rate of the RDS is: k 3 [CO∗][O∗] k −3 [CO2 ][∗]2 r= − [∗]o [∗]o (2) The adsorption of CO on the surface. the desorption of H2 from the surface and the dissociation of water are all assumed to be equilibrated. substitute equations (5) and (3) into equation (2).18 . Therefore the following relationships are used. K2 = 3 and K 4 = [CO ][∗] [∗] [ H 2 O] [ H ∗] 2 (3) The site balance for this mechanism is: [∗]o = [∗] + [CO∗] + [O∗] + [ H ∗] (4) After substituting the equilibrium expressions into the site balance and rearranging 5.[∗] = [∗]o k [ H O] + k − 2 [CO2 ] 1+ 1 2 k 2 [CO ] + k −1 [ H 2 ] (5) Next. K1 = [ H 2 ][∗] 2 [CO∗] [ H ∗] 2 [O∗] .

19 (2) .[∗] = [∗]o K K [ H O] [ H ]1 / 2 1 + K 1 [CO ] + 2 4 2 + 21 / 2 [H 2 ] K4 (5) Substituting equation (5) and the equilibrium expressions into equation (2) results in the following rate expression: r= K1 K 2 K 4 k 3 [CO ][ H 2 O][∗]o − k −3 [CO2 ][∗]o [ H 2 ]  K K [ H O] [ H ]1 / 2  [ H 2 ]1 + K1[CO ] + 2 4 2 + 21 / 2  [H 2 ] K4   2 (6) Exercise 12: The overall reaction is the following CH3CH2CHO + H2 = CH3CH2CH2OH part a) A reasonable sequence of reaction steps for this reaction is the following: CH3CH2CHO + ∗ H2 + 2∗ CH3CH2CHO∗ 2H∗ CH3CH2CHO∗ + H∗ CH3CH2CH2O∗ + ∗ CH3CH2CH2O∗ +H∗ CH3CH2CH2OH∗ + ∗ CH3CH2CH2OH∗ (1) ∗ + CH3CH2CH2OH part b) The rate of consumption of CH3CH2CHO is (since the adsorption of CH3CH2CHO is the RDS): − d [CH 3CH 2 CHO] = r = k1[CH 3CH 2 CHO ][∗] − k −1[CH 3CH 2 CHO*] dt 5.

[CH 3 CH 2 CHO∗][ H ∗] (3) [CH 3 CH 2 CH 2 OH ∗][∗] K4 = [ H ∗][CH 3CH 2 CH 2 O∗] and [∗][CH 3CH 2 CH 2 OH ] K5 = [CH 3 CH 2 CH 2 OH ∗] The site balance for this mechanism is the following: [∗]o = [∗] + [CH 3CH 2 CHO∗] + [ H ∗] + [CH 3CH 2 CH 2 O∗] + [CH 3 CH 2 CH 2 OH ∗] (4) After substituting the equilibrium expressions into the site balance and then plugging the result into the rate expression in equation (2). Therefore. H2 must be large and that of CH3CH2CH2OH must be small. the rate of consumption of CH3CH2CHO is the following:  k [CH 3 CH 2 CH 2 OH ]   k1 [CH 3CH 2 CHO ] − −1 [∗]o K K K K H [ ] − d [CH 3 CH 2 CHO ] 5 4 3 2 2   = CH CH CH OH [CH 3CH 2 CH 2 OH ] [ ] [CH 3 CH 2 CH 2 OH ] dt 3 2 2 1+ + K 21 / 2 [ H 2 ]1 / 2 + + 1/ 2 1/ 2 K 5 K 4 K 3 K 2 [H 2 ] K5 K 4 K 5 K 2 [H 2 ] part c) If PH 2 (or [H2]) is large and PCH 3CH 2CH 2OH (or [CH3CH2CH2OH]) is small. all other steps are quasi-equilibrated. 5. in order to reduce to r = kPprop PH02.Since the adsorption of CH3CH2CHO is the RDS. the reaction rate reduces to k [∗] [CH CH CHO ] r = 1 o 1 / 2 3 12/ 2 K 2 [H 2 ] Therefore. K2 = [ H ∗] 2 [ H 2 ][∗] 2 K3 = [CH 3 CH 2 CH 2 O∗][∗] .20 .5 . the following equilibrium relationships are used.

[2O − 2 ] = [∗]o k [ RH 2 ] 1+ 1 k 2 [O2 ] (4) Lastly. r = r1 = r2 = k1[ RH 2 ][2O −2 ] = k 2 [O2 ][2 ávac] (1) Solving for the concentration of vacancy pairs yields. [2ávac]= k1 [ RH 2 ][2O −2 ] k 2 [O2 ] (2) The site balance for this system is [∗]o = [2O −2 ] + [2ávac] (3) After substituting the expression for the concentration of vacancy pairs into the site balance and solving for the concentration of O-2.21 . the rate expression in equation (5) becomes 1 1 1 = + r k1[∗]o [ RH 2 ] k 2 [∗]o [O2 ] where K1 = k1[∗]o and K2 = k2[∗]o 5. r= k1[ RH 2 ][∗]o k [ RH 2 ] 1+ 1 k 2 [O2 ] (5) After simplification. substitute equation (4) into the rate expression in equation (1).Exercise 13: Use the steady state approximation since we cannot assume that one step is the RDS. Therefore.