Reaction Rate Laws

Rate Laws & Reaction Order

Chemical Equilibrium
k
A + B + C + ... −−→ D + E + F + ...
Dr. Md. Zahurul Haq, Ph.D., CEA, FBSME, FIEB

d [A]
Professor • Reaction Rate (RR) = = −k[A]a [B]b [C ]c · · ·
Department of Mechanical Engineering dt
Bangladesh University of Engineering & Technology (BUET) a, b, c, · · · are reaction orders wrt. A, B, C , · · · ,
Dhaka-1000, Bangladesh
k is the rate coefficient of the reaction,
zahurul@me.buet.ac.bd the sum of all the exponents is the overall reaction rate.
http://zahurul.buet.ac.bd/
• If some species are in excess, [B], [C ], · · · remains constant,
ME 6101: Classical Thermodynamics d [A]
RR = = −k[A]a
http://zahurul.buet.ac.bd/ME6101/ dt
• If the time behaviour is measured, the reaction order can be
determined.
© Dr. Md. Zahurul Haq (BUET) Chemical Equilibrium ME 6101 (2022) 1 / 14 © Dr. Md. Zahurul Haq (BUET) Chemical Equilibrium ME 6101 (2022) 2 / 14

Reaction Rate Laws Reaction Rate Laws

[A]t Relation of Forward & Reverse Reactions

• For first-order systems (a = 1): = −k(t − t0 ) ln
[A]0
[A]0 & [A]t denote the concentration of species A at time t0 and t,
respectively. k
1 1 A + B + C + ... −−→ D + E + F + ...
• For second-order systems (a = 2): − = k(t − t0 )
[A]t [A]0
1 1
• For third-order systems (a = 3): − = 2k(t − t0 ) d [A]
[A]2t [A]20 • Forward reaction rate for production of A, = −kf [A]a [B]b [C ]c · · ·
dt
 064567557892
4 d [A]
 0124567557892
4

• Reverse reaction rate for production of A,
dt
= kb [D]d [E ]e [F ]f · · ·

 • At chemical equilibrium, forward and backward reaction rates are same
and no net reaction can be observed.
⇒ −kf [A]a [B]b [C ]c · · · = kb [D]d [E ]e [F ]f · · ·
0 ⇒ Equilibrium constant (based on concentration), Kc

T1256 Kc ≡ kkbf = [D]
d [E ]e [F ]f

[A]a [B]b [C ]c

© Dr. Md. Zahurul Haq (BUET) Chemical Equilibrium ME 6101 (2022) 3 / 14 © Dr. Md. Zahurul Haq (BUET) Chemical Equilibrium ME 6101 (2022) 4 / 14
 Reaction Rate Laws Reaction Rate Laws

Temperature Dependence of Rate Coefficients Global One-step Reaction

 
    Ea /Ru
Arrhenius law: k = Ao exp − EaT/Ru = Ao exp − TTa RR = Ao exp − [Fuel ]a [O2 ]b
T
Ao ≡ pre-exponential factor
Ea ≡ activation energy, corresponds to an energy barrier which 0123 45 6789
73 3 7 
has to be overcome during reaction.  5  5 
 5 5 5 
Ta ≡ activation temperature, Ta ≡ Ea /Ru  5 5 5 
41  5 5 5 
40
33
5 5 5 5 
 33  5 5 5 
31  5 5 5 
 30 33  5 5 5 
012345

 5 5 5 

6789

43
62789719
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 20 5 5 5 5 
1
3  5 5 5 
3 89
 5 5 5 
0
0 051 2 251 3 351 4 451  55 5 5 
62789183 1792 T1258    5 5 5 
7 !"#$ %45&8 3
7'$
T1257
T1259

© Dr. Md. Zahurul Haq (BUET) Chemical Equilibrium ME 6101 (2022) 5 / 14 © Dr. Md. Zahurul Haq (BUET) Chemical Equilibrium ME 6101 (2022) 6 / 14

Reaction Rate Laws Reaction Rate Laws

Example: Methane Combustion at 1800 K Time Scales in Chemically Reacting Flow

987
6789
2 92 27
6789
2 92
CH4 + 2 (O2 + 3.76 N2 ) −−→ CO2 + 2 H2 O + 7.52 N2  
6789
2 92

9
3867 0112
!"9
98726#
 
• RR = Ao exp − EaT/Ru [Fuel ]a [O2 ]b 01342
76989$769
6789
2 92

 

• A0 = 1.3 × 109 mol/cm3 6789

2 92
01352 626
6 99
• Ea = 48.4 kcal/mol, Ru = 1.987 cal/mol.K

013)2
• a = −0.3, b = 1.3, [O2 ] = 2[CH4 ]
%26
6789
2 92

• d[CH 4]
= RR = 1.3 × 109 exp − 24358 −0.3 (2[CH ])1.3
!9&7 7
98726#


1800 [CH4 ]
dt 4
'$9
6
269$
26692

⇒ d[CH4 ]
dt = −4245.3[CH4 ] 67
9&7 77( 013*2
[CH4 ]
⇒ = exp(−4245.3t)
[CH4 ]0
• Reduction to 5%, exp(−4245.3t) = 0.05 → t = 0.71 ms T1316 6
9
9&7 769$
© Dr. Md. Zahurul Haq (BUET) Chemical Equilibrium ME 6101 (2022) 7 / 14 © Dr. Md. Zahurul Haq (BUET) Chemical Equilibrium ME 6101 (2022) 8 / 14
 Reaction Rate Laws Chemical Equilibrium

Pressure Dependence of Rate Coefficients Criterion for Chemical Equilibrium

• dSsys > δQ
T → dSsys > 0 for δQ = 0
• δQ − PdV = dU → dU + PdV − TdS 6 0
  • G ≡ H − TS → dG = dH − TdS − SdT
Ea /Ru (dG )P,T = dU + PdV − TdS → (dG )P,T 6 0
RR = Ao exp − [Fuel ]a [O2 ]b •
T 
P/Ru (a+b)
   
Ea /Ru
= Ao exp − [Xfuel ]a [XO2 ]b ∝ P (a+b)
T T

1 1
• For one-step combustion chemistry model, (a + b) is always positive, 1
ranging from 1.0 to 1.75.
5 955
• When the pressure of a combustion system is doubled, the reaction
856 
rate can increase threefold for the case a + b = 1.75.
0112 7 47 0112
4899
8535
95 3456789

T1319

Fixed mass reactions at fixed P & T

© Dr. Md. Zahurul Haq (BUET) Chemical Equilibrium ME 6101 (2022) 9 / 14 © Dr. Md. Zahurul Haq (BUET) Chemical Equilibrium ME 6101 (2022) 10 / 14

Chemical Equilibrium Chemical Equilibrium

Equilibrium Constant, Kp X 
Pi

• νC gCo ,T + o
νD gD,T − o
νA gA,T − o
νB gB,T = −Ru T νi ln
P0
R→P

01234567 (PC /P0 )νC (PD /P0 )νD

 
⇒ ∆GTo = −Ru T ln = −Ru T ln(KP )
3829
1 (PA /P0 )νA (PB /P0 )νB
  dNA A + dNB B −−→ dNC C + dND D o
h i
• KP = exp − ∆G T

9616
Ru T
• dNA = −ǫνA , dNB = −ǫνB
9616
(PC /P0 )νC (PD /P0 )νD
• Equilibrium constant, KP ≡ (PA /P0 )νA (PB /P0 )νB
• dNC = +ǫνC , dND = +ǫνD
9616 • ǫ is a proportionality constant. • KP = e (−∆GT /Ru T ) =
o
e −∆H o /R T ∆S o /R
u ė u

9616 • For KP > 0, which favours products, ∆H o should be negative,

T1320 exothermic reaction.
X X Pi
• Gmix = Ni gi ,T = Ni (gio,T + Ru T ln( )) • For gaseous mixture, Pi = Xi P, and if ∆ν = νC + νD − νA − νB ,
P0
X νC X νD P ∆ν NCνC NDνD P/P0 ∆ν
   
R→P R→P
• For fixed T & P, equilibrium condition: ⇒ KP = CνA DνB = νA νB
XA XB P0 NA NB NT
P
⇒ dGmix = 0 = R→P dNi (gio,T + Ru T ln( PP0i )) • NT is the total number of moles present in the reaction vessel.

© Dr. Md. Zahurul Haq (BUET) Chemical Equilibrium ME 6101 (2022) 11 / 14 © Dr. Md. Zahurul Haq (BUET) Chemical Equilibrium ME 6101 (2022) 12 / 14
 Chemical Equilibrium Chemical Equilibrium

Illustrative Example: Effects of pressure and inert-addition on equilibrium

Illustrative Example: Dissociation of CO2 at 2500 K, 10 atm composition
CO2 −−
↽ −− CO + 12 O2
⇀
T = 298 K 1 0 0 1 atm 5 atm N2 addition
T = 2500 K 1 - α α α/2
o
• ∆G2500 = [gCO + 0.5gO2 − gCO2 ]2500
⇒ KP = exp(−∆GTo /Ru T ) = 0.0363
0.5
 1+0.5−1
• KP = XCO XO2
XCO2
P
P0
  1/2
α α/2 T1321 T1322 T1323
1+α/2 1+α/2
⇒ 0.036 = 
1−α
 100.5 • x = 0.34 • x = 0.193 • x = 0.47
1+α/2

⇒ α = 0.06205 → XCO = 0.0602 T1213 • y = 0.67 • y = 0.5965 • y = 0.736

• z = 0.66 • z = 0.807 • z = 0.53

© Dr. Md. Zahurul Haq (BUET) Chemical Equilibrium ME 6101 (2022) 13 / 14 © Dr. Md. Zahurul Haq (BUET) Chemical Equilibrium ME 6101 (2022) 14 / 14