CHEMICAL KINETICS

Thermodynamics and thermochemistry: energy changes associated with chemical reactions, direction of spontaneous processes, but not the time needed for the completion of reaction. Experience: a spontaneous process does not necessarily occur within measurable time N2 (g) + 3H2 (g) 2NH3 (g)

REACTION RATES
only for spontaneous chemical reactions concentration change Reaction rate = time change

G = 33 kJ/mol

reaction rate = increase in the concentration of a product per unit time or decrease in the concentration of a reactant per unit time Reaction rates are always positive.

This reaction (ammonia synthesis) is spontaneous at room temperature, but does not occur in billions of years. Chemical kinetics: study of reaction rates and mechanisms

REACTION RATES
2 N2O5 (g) 4 NO2 (g) + O2 (g) Rate of O2 formation: [O2] t =
Conc. of O2 at time t2 Conc. of O2 at time t1

RATE LAWS AND REACTION ORDER

rate law: gives the dependence of the reaction rate on reactant (and sometimes other) concentrations Usual form of a rate law for a general reaction: a A + b B Products

t 2 t1

Rate of NO2 formation = 4 Rate of O2 formation

General rate of reaction = 1 [N2O5 ] 1 [NO2 ] 1 [O2 ] = = 2 4 t 1 t t

Rate = k [ A ]m [B]n

reactant: negative product: positive

stoichiometric coefficients from the chemical equation

Rate = k [ A ]m [B]n
k: rate constant m: reaction order with respect to A n: reaction order with respect to B (m + n): overall reaction order, the sum of all individual reaction orders Reaction orders: NOT the same as stoichiometric coefficients can only be determined experimentally very often whole numbers

H2 + I2 2 HI

rate = k1[H2][I2]

reaction order with respect to H2: 1 first-order reaction order with respect to I2: 1 first-order overall reaction order: 2 second-order Br2 + HCOOH CO2 + 2H+ + 2Br

rate = k2[Br2]

reaction order with respect to Br2: 1 first-order reaction order with respect to HCOOH: 0 zeroth-order overall reaction order: 1 first-order

BrO3 + 5Br + 6H+ 3Br2 + 3H2O rate = k3[BrO3][Br][H+]2 reaction order with respect to BrO3: 1 first-order reaction order with respect to Br: 1 first-order reaction order with respect to H+: 2 second-order overall reaction order: 4 fourth-order CH3CHO CH4 + CO

RATE CONSTANTS
unit of rate: Ms1 unit of rate constant: depends on the overall order of the rate law overall reaction order zeroth-order half-order first-order unit of rate constant Ms1 Ms1 s1 Ms1 M1s1 M2s1 M3s1

rate = k4[CH3CHO]3/2

three-halves order second-order third-order fourth-order

reaction order with respect to CH3CHO: 3/2 three-halves order overall reaction order: 3/2 three-halves order

FIRST-ORDER REACTION
Br2 + HCOOH CO2 + 2H+ + 2Br integrated rate law: rate = k[Br2]

exponential form

logarithmic form

[Br 2 ] (M)

Br2 limiting reactant, HCOOH in excess

ln [Br 2]/[Br 2 ]0

slope = k

exponential curve

[Br2 ] = [Br2 ]0 e kt [Br2 ] = kt [Br2 ]0

exponential form

ln

logarithmic form
Time (s)

Time (s)

HALF-LIFE
half-life (t): the time required for the reactant
concentration to drop to one-half of its initial value first-order reactions: the half-life is independent of the initial concentration, characteristic of the reaction

REACTION MECHANISMS
reaction mechanism: The sequence of reaction steps that defines the pathway from reactants to products elementary reaction: a simple chemical reaction which describes an individual molecular event, one step in a reaction mechanism intermediate: a species that is formed in one step of a reaction mechanism and consumed in a subsequent step 2 N2O (g) 2 N2 (g) + O2 (g) N2O (g) N2 (g) + O (g) overall reaction elementary reaction

ln 2 0.693 = t = k k
other reactions: the half-life is dependent on the initial concentration

N2O (g) + O (g) N2 (g) + O2 (g) elementary reaction intermediate

MOLECULARITY
molecularity of an elementary reaction: the number of molecules (or atoms) on the reactant side

REACTION RATE AND TEMPERATURE

Everyday experience: the rates of chemical reactions increase markedly with increasing temperature rule of thumb: reaction rates tend to double or triple when the temperature is increased by 10 C The number of collisions between molecules increases with temperature, but: there are too many collisions, only a small fraction of collisions leads to reaction reaction rates increase much more rapidly with temperature than collision numbers

unimolecular: involves one reactant molecule (common) O3* (g) O2 (g) + O (g) bimolecular: reaction by energetic collisions of two reactant molecules (common) O3 (g) + O (g) 2 O2 (g) termolecular: involves three reactant molecules (very rare) O (g) + O (g) + M (g) O2 (g) + M(g)

Arrhenius plot
ARRHENIUS EQUATION
dependence of rate constants on temperature Svante Arrhenius: Swedish chemist, Nobel prize in 1903 (electrolytic theory), proposed equation in 1889 rate constant slope: Ea/R

k = Ae E a / RT
frequency factor activation energy

linearized form

ln k = A

Ea 1 R T

ln k

1/T (1/K)

Energy profile of a reaction

Transition state

CATALYSIS
reaction rates may depend on concentrations other than those of the reactants

potential energy

Ea Reactants

catalyst: a substance that increases the rate of a reaction without being consumed in it 2 KClO3 (s) 2 KCl (s) + 3 O2 (g) catalyst: MnO2 (s) autocatalysis: the catalyst is the product of the reaction

Products

reaction progress

2 H2O2 (aq) 2 H2O (l) + O2 (g) H2O2 + I H2O + IO H2O2 + IO H2O + I + O2 catalyst

overall reaction elementary reaction elementary reaction

Homogeneous catalysis The catalyst exists in the same phase as the reactants

Example 3 O2 (g) 2 O3 (g) overall reaction elementary step elementary step elementary step O2 (g) + NO (g) NO2 (g) + O (g) NO2 (g) NO (g) + O (g) O (g) + O2 (g) O3 (g) catalyst intermediate intermediate

A catalyst accelerates the rate of a reaction by making available a new and more efficient mechanism for conversion of reactants to products. enzymes: large molecules in biological systems that are very efficient and specific catalysts

Heterogeneous catalysis The catalyst exists in a different phase from that of the reactants Very important industrial processes on very large scales.

EXPLOSIONS
Thermal explosions: an exothermic chemical reaction begins the heat produced increases the temperature the reaction rate increases

Examples 2 SO2 (g) + O2 (g) 2 SO3 (g) N2 (g) + 3H2 (g) 2NH3 (g) catalyst: V2O5 (s) catalyst: Fe, Al2O3 (s)

even more heat is produced, even more increase in temperature reaction rate increases even more....

CO (g) + 2H2 (g) CH3OH (l) catalyst: ZnO, Cr2O3 (s) Most potentially explosive chemical reactions can be carried out smoothly if the excess heat is absorbed.

CHEMICAL EQUILIBRIUM
Most chemical reactions go to 'completion' = the reaction persists until the limiting reagent is completely used up Some chemical reactions do not reach completion, the reaction stops before the limiting reagent is completely used up

CHEMICAL EQUILIBRIUM =
the state reached when the concentrations of reactants and products remain constant over time

earlier example: evaporation of a liquid and vapor pressure melting of a solid

the state of equilibrium is reached

equilibrium mixture: a mixture of reactants and products in the equilibrium state

N2O4 (g)

2 NO2 (g)
concentration (M)

0.08

reaction started from pure N2O4 NO2 appears reaction started from pure NO2 N2O4 appears

0.06

0.04

the reaction is REVERSIBLE: it can proceed in both directions depending on the concentration of reactants or products forward reaction: upper arrow, left to right reverse reaction: lower arrow, right to left

N2O4

0.02
NO2

0 time (s)

Chemical equilibrium
0.08
DYNAMIC

concentration (M)

0.06

the forward and reverse reactions do not stop, but they have exactly the same rate no change in the concentrations of products or reactants occurs N2O4 UNIVERSAL

0.04

0.02
NO2

0 time (s)

strictly speaking, all chemical reactions are reversible and lead to equilibrium. In 'practically complete' reactions the equilibrium mixture contains so small amounts of reactants that they are not detectable

EQUILIBRIUM CONSTANT
rate of reaction (M-1s-1)
forward rate 1 N2O4 (g) experience reverse rate
2 [NO2 ]eq
1 [N2O 4 ]eq

2 NO2 (g)

Kc =

concentration in equilibrium this expression in the state of equilibrium is independent of the initial concentrations

time (s)

LAW OF MASS ACTION

The equilibrium constant is the number obtained by multiplying the equilibrium concentrations of all the products and dividing by the equilibrium concentrations of all the reactants, with the concentration of each substance raised to the power of its coefficient in the balanced chemical equation.

N2 (g) + 3H2 (g)

[N2]eq = 3.0 102 M [NH3]eq = 1.6 102 M

2 NH3 (g)

equilibrium concentrations at 500 K: [H2]eq = 3.7 102 M

Kc =

[NH ]

2 3 eq 3 2 eq

aA+bB

cC+dD
products reactants

[N2 ]eq [H ]

0.016 2 = 1.7 10 2 M2 0.030 0.037 3

Kc =

[C ]c [D ]d eq eq
a b [ A ]eq [B]eq

Kc is independent of initial reactant and product concentrations Kc depends on temperature Kc has different units depending on the chemical equation

For gas reactions, e.g.

HETEROGENEOUS EQUILIBRIA
2 NH3 (g) CaCO3 (s) CaO (s) + CO2 (g)

N2 (g) + 3H2 (g)

the Kp equilibrium constant can be defined as

Kp =

( pNH3 )2 pN2 ( pH2 )3

Kc ' =

[CO2 ]eq [CaO ]eq [ CaCO3 ]eq

???

where p indicates partial pressure for N2 as an ideal gas change in number of moles solids: the concentration is independent of the amount of substance present and is constant

pN2V = nN2RT [N2] = nN2/V = pN2/RT

Kp =

( pNH3 )2 pN2 ( pH2 )3

2 [NH3 ]eq (RT )2 3 [N2 ]eq [H2 ]eq (RT ) 4

= K c (RT )

Kc = Kc '

[ CaCO 3 ]eq [ CaO ]eq

constants

= [CO2 ]eq

K p = pCO2

CaCO3 (s)

Ca2+ (aq) + CO32 (aq)

2

REACTION QUOTIENT
H2 (g) + I2 (g) 2 HI (g)

K c = [Ca 2 + ][CO3 ]
concentrations of pure solids and pure liquids are not included when writing an equilibrium equation because their concentrations are constants that are incorporated into the value of equilibrium constants

Kc =

2 [HI]eq

[H2 ]eq [I2 ]eq

Qc =

[HI]2 [H2 ][I2 ]

equilibrium constant: only in equilibrium

reaction quotient: in any state

The direction of the net reaction: only the concentrations of gases and the concentrations of solutes in solutions are included if Qc = Kc, no net reaction occurs (equilibrium) if Qc < Kc, net reaction goes from left to right if Qc > Kc, net reaction goes from right to left

ALTERING THE COMPOSITION OF AN EQUILIBRIUM MIXTURE

concentration of reactants and products pressure or volume temperature

LE CHATELIER'S PRINCIPLE
General, qualitative rule that predicts the way the composition of an equilibrium mixture changes upon external influence

Le Chatelier's principle: if a stress is applied to a reaction mixture at equilibrium, net reaction occurs in the direction that relieves the stress

A catalyst never affects the composition of the equilibrium mixture, it only increases the rate at which equilibrium is reached.

stress = change in concentration, pressure, volume, or temperature that disturbs the equilibrium

N2 (g) + 3H2 (g)

2 NH3 (g)

CHANGES IN CONCENTRATION

equilibrium concentrations at 500 K: [N2]eq = 3.0 102 M [NH3]eq = 1.6 102 M

2 [NH3 ]eq

[H2]eq = 3.7 102 M

the concentration stress of an added reactant or product is relieved by net reaction in the direction that consumes the added substance the concentration stress of a removed reactant or product is relieved by net reaction that replenishes the removed substance

Kc =

[N2 ]eq [H ]

3 2 eq

0.016 2 = 1.7 10 2 M2 0.030 0.037 3

some NH3 is removed so that [NH3] = 1 103 M

Qc = [NH3 ]2 0.0012 = = 6.6 10 1 M2 [N2 ][H2 ]3 0.030 0.037 3

< Kc

reaction goes from left to right, more NH3 is produced

N2 (g) + 3H2 (g)

2 NH3 (g)

CHANGES IN PRESSURE AND VOLUME

an increase in pressure by reducing the volume will bring about net reaction in the direction that decreases the number of moles of gas a decrease in pressure by enlarging the volume will bring about net reaction in the direction that increases the number of moles of gas If the reaction does not involve a change in the number of moles of gases, e.g. H2 (g) + I2 (g) 2 HI (g) a change in pressure does not influence the composition of the equilibrium mixture

Kc =

[NH ]

2 3 eq 3 2 eq

[N2 ]eq [H ]

0.016 2 = 1.7 10 2 M2 0.030 0.037 3

some N2 is added so that [N2] = 3.0 101 M

[NH3 ]2 0.016 2 Qc = = = 1.7 101 M2 [N2 ][H2 ]3 0.30 0.037 3

< Kc

reaction goes from left to right, some of the extra N2 is consumed

N2 (g) + 3H2 (g)

2 NH3 (g)

N2 (g) + 3H2 (g)

2 NH3 (g)

Kc =

[NH ]

2 3 eq

3 [N2 ]eq [H2 ]eq

0.016 2 = 1.7 10 2 M2 0.030 0.037 3

Kc =

[NH ]

2 3 eq

3 [N2 ]eq [H2 ]eq

0.016 2 = 1.7 10 2 M2 0.030 0.037 3

the volume is compressed to one half of its original value all concentrations double
Qc = [NH3 ]2 0.032 2 = = 4.2 101 M2 [N2 ][H2 ]3 0.060 0.074 3

the volume is doubled all concentrations drop to one half of the initial values
Qc = [NH3 ]2 0.0080 2 = = 6.7 10 2 M2 > [N2 ][H2 ]3 0.015 0.0185 3

< Kc

Kc

reaction goes from left to right, number of gas molecules decreases, pressure decreases

reaction goes from right to left, number of gas molecules increases, pressure increases

CHANGES IN TEMPERATURE
The equilibrium constant (not only the composition of the equilibrium mixture) is dependent on temperature.

N2 (g) + 3H2 (g)

1.00E+08

2 NH3 (g) H= 92.2 kJmol1

exothermic
-2 K c (M )

the equilibrium constant for an exothermic reaction (negative H) decreases as the temperature increases the equilibrium constant for and endothermic reaction (positive H) increases as the temperature increases

1.00E+04

1.00E+00

1.00E-04 200

400

600 T (K)

800

1000

N2 (g) + 3H2 (g)

2 NH3 (g) H= 92.2 kJmol1

N2 (g) + 3H2 (g)

2 NH3 (g) H= 92.2 kJmol1

at 500 K: Kc = 1.7 102 M2

at 500 K: Kc = 1.7 102 M2

cooling to 400 K all concentrations remain the same initially new Kc = 3.9 104 M2 > Qc = 1.7 102 M2

heating to 600 K all concentrations remain the same initially new Kc = 4.2 100 M2 < Qc = 1.7 102 M2 reaction goes from right to left, heat is absorbed, temperature decreases

reaction goes from left to right, heat is produced, temperature increases

Summary:

N2 (g) + 3H2 (g)

2 NH3 (g) H= 92.2 kJmol1

formation of ammonia is favored by high pressure high initial reactant concentrations low temperature Problem: at low temperature the reaction rate is also low, too much time is needed for the reaction INDUSTRIAL PROCESS: moderately high temperature and very high pressure, a compromise that ensures a good yield and acceptable reaction time