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Kinetics/Rate of Reaction
applies to the speed of a reaction, the
change in concentration of product
appearing (or of reactant disappearing)
per unit time.
Chemical Kinetics
A B
D[A] D[A] = change in concentration of A over
rate = -
Dt time period Dt
D[B] D[B] = change in concentration of B over
rate =
Dt time period Dt
Because [A] decreases with time, D[A] is negative.
3
A B
D[A]
rate = -
Dt
D[B]
rate =
Dt
4
Reaction Rates and Stoichiometry
2A B
1 D[A] D[B]
rate = - rate =
2 Dt Dt
aA + bB cC + dD
5
Factors Influencing Rate of Reaction
1. Nature of reactants
3. Temperature
4. Catalysts
Factors Influencing Rate of Reaction
1. Nature of reactants
e.g. Na(s) + H2O reacts violently
Fe(s) + H2O rusts slowly
Au(s) + H2O doesnt tarnish even after years of
exposure
effective collision
ineffective collision
11
Transition State:
Activated Complex or Reaction Intermediates
Activation Energy, Ea
the minimum energy required for reactant
molecules to undergo effective collision
+
A+B AB+ C+D
Exothermic Reaction Endothermic Reaction
Reactions with large Ea = Slow Reactions (only few molecules are able to meet
the energy requirement)
Reactions with small Ea = Rapid Reactions (large fraction of molecules have
sufficient energy to reach transition state)
Factors Influencing Rate of Reaction
3. Effect of Temperature
INC T INC reaction rate
A + B C + D
kf [A][B] = kb [AB]
kf [AB]
= K=
kb [A][B]
Equilibrium is a state in which there are no observable
changes as time goes by.
Physical equilibrium
20
N2O4 (g) 2NO2 (g)
equilibrium equilibrium
equilibrium
Start with NO2 Start with N2O4 Start with NO2 & N2O4
21
constant
22
N2O4 (g) 2NO2 (g)
[NO2]2
K= = 4.63 x 10-3
[N2O4]
aA + bB cC + dD
[C]c[D]d
K= Law of Mass Action
[A]a[B]b
23
[C]c[D]d
K= aA + bB cC + dD
[A]a[B]b
Equilibrium Will
K >> 1 Lie to the right Favor products
K << 1 Lie to the left Favor reactants
24
Homogenous equilibrium applies to reactions in which all
reacting species are in the same phase.
2
PNO
[NO2]2
Kc = Kp =
2
[N2O4] PN2O4
In most cases
Kc Kp
aA (g) + bB (g) cC (g) + dD (g)
Kp = Kc(RT)Dn
[CH3COO-][H3O+]
Kc = [H2O] = constant
[CH3COOH][H2O]
[CH3COO-][H3O+]
Kc = = Kc [H2O]
[CH3COOH]
26
Write expressions for Kc, and KP if applicable, for the following
reversible reactions at equilibrium:
27
Solution
(a) Because there are no gases present, KP does not apply and
we have only Kc.
+ -
' [H 3 O ][F ]
Kc =
[HF][H 2 O]
[H 3O + ][F - ]
Kc =
[HF]
28
2 2
(b) [NO 2 ] PNO
Kc = Kp = 2
[NO]2 [O 2 ] 2
PNO PO2
'
(c) The equilibrium constant K c is given by
30
Solution
First, we write KP in terms of the partial pressures of the
reacting species
PPCl3 PCl2
Kp =
PPCl5
[CaO][CO2]
Kc = [CaCO3] = constant
[CaCO3] [CaO] = constant
[CaCO3]
Kc = [CO2] = Kc x Kp = PCO2
[CaO]
32
CaCO3 (s) CaO (s) + CO2 (g)
PCO 2 = Kp
33
HETEROGENEOUS Rxns take place at a surface or
boundary between 2 phases
e.g. Rusting of iron:surface of Fe reacts with O2
CuSO4(aq) + Zn ZnSO4(aq) + Cu
BaCl2 + Na2SO4 BaSO4(s)
35
Strategy
Solution
KP = PCO2
= 0.236
36
(b) Recall,
KP = Kc(0.0821T)n
37
[C][D] [E][F]
A+B C+D Kc Kc = Kc=
[A][B] [C][D]
C+D E+F Kc
[E][F]
A+B E+F Kc Kc =
[A][B]
Kc = Kc x Kc
38
N2O4 (g) 2NO2 (g) 2NO2 (g) N2O4 (g)
[NO2]2 [N2O4] 1
K= = 4.63 x 10-3 K = = = 216
[N2O4] [NO2]2 K
39
Writing Equilibrium Constant Expressions
The concentrations of the reacting species in the
condensed phase are expressed in M. In the gaseous
phase, the concentrations can be expressed in M or in atm.
The concentrations of pure solids, pure liquids and solvents
do not appear in the equilibrium constant expressions.
The equilibrium constant is a dimensionless quantity.
In quoting a value for the equilibrium constant, you must
specify the balanced equation and the temperature.
If a reaction can be expressed as a sum of two or more
reactions, the equilibrium constant for the overall reaction is
given by the product of the equilibrium constants of the
individual reactions.
H2O + H2O H3O+ + OH-
Auto-ionization [H3O+][OH-]
of Water K = -----------------
[H2O]2
2 + -
Kw = K [H2O] = [H3O ][OH ] = 1.0 x 10-14
Ion-product constant
for water
Calculate the hydronium and hydroxide
ion concentrations of pure water at 25C
and 100C.
Example 3-15
2-42
Because OH and H3O+ are formed only from the
dissociation of water, their concentrations must be
equal:
Substitution into:
Kw = [H3O+][OH-] = 1.0 x 10-14
Example 3-15
2-43
At 25C,
Example 3-15
2-44
Ba(IO3)2 (s) + H2O (l) Ba2+(aq) + 2 IO3- (aq)
Solubility- [Ba2+][IO3-]2
Product Constant K = ------------------------
[Ba(IO3)2 (s)][H2O]
Example 3-17
2-46
Example 3-17
1
= [IO ]
2 3
2-47
Since:
Example 3-17
2-48
Example 3-17
2-49
How Does a Common Ion Affect the
Solubility of a Precipitate?
3E-3
The commonion effect is a mass-action effect predicted
Important from the Le Chtelier principle.
Equilibrium
Constants in The common-ion effect is responsible for the
reduction in solubility of an ionic precipitate when a
Analytical soluble compound combining one of the ions of the
Chemistry precipitate is added to the solution in equilibrium with
the precipitate.
2-50
Calculate the molar solubility of Ba(IO3)2 in a
Solubility- solution that is 0.0200 M in Ba(NO3)2 .
Product Ba(IO3)2 (s) Ba2+(aq) + 2 IO3-
Constant 2+
+ Ba (aq) (from Ba(NO3)2 )
COMMON-ION
EFFECT
Example 3-18
2-51
Example 3-18
2-52
Ordinarily, we consider an assumption of this type to
be satisfactory if the discrepancy is less than 10%.
Finally, then,
Example 3-18
2-53
Acid-Base Equilibrium in Aqueous Solution
Acid Dissociation Constant
HC2H3O2 + H2O H3O+ + C2H3O2-
[H3O+][C2H3O2-]
K = ----------------------
[H2O][HC2H3O2]
[H3O+][C2H3O2-]
Ka = K [H2O] = ----------------------
[HC2H3O2]
Acid-Base Equilibrium in Aqueous Solution
[NH4+][OH-]
K = -----------------
[H2O][NH3]
[NH4+][OH-]
Kb = K [H2O] = ----------------
[NH3]
Dissociation Constants for Conjugate
Acid/Base Pairs
3E-3
Important
Equilibrium
Constants in
Analytical
Chemistry
(3-16)
2-56
Dissociation Constants for Conjugate
Acid/Base Pairs
2E-3
Important
Equilibrium
Constants in
Analytical
Chemistry To obtain a dissociation constant for a base, look up in
Appendix 2 the dissociation constant for its conjugate
acid and then divide this number into 1.00 1014.
2-57
What is Kb for the equilibrium (refer to
Appendix 2 for the Ka value of HCN)?
Example 3-20
2-58
Exercises
1. Expression for Equilibrium Constant
a. HCN + H2O H+ + CN-
b. NH4OH + H2O NH4+ + OH-
c. H2S + H2O 2 H+ + S2-
d. Hg22+ + 2 Fe3+ 2 Fe2+ + Hg2+
e. CO2 + H2 CO + H2O
f. 2 NO2 2 NO + O2
g. 3 H2 + N2 2 NH3
Manipulations of Equilibrium Constants
Actual example (T=25)
PLAN: We have to find the concentrations of all species at equilibrium and then
substitute into a Kc expression.
SOLUTION: All concentrations must be recalculated as M, so [CO] = 0.250/0.125L
x
1.56 = = +/- 1.25
2.00-x
PLAN: After finding the concentration of starting material, write the expressions for
the equilibrium concentrations. When solving for the remaining amount of
reactant, see if you can make an assumption about the initial and final
concentrations which could simplifying the calculating by ignoring the solution
to a quadratic equation.
(x) (x)
[CO][Cl2] (a) Kc = 8.3x10-4 =
Kc = (0.500-x)
[COCl2]
assume x is << 0.500 so that we can drop x in the denominator
(x) (x) 4.15x10-4 = x2 x 2 x 10-2
8.3x10-4 =
(0.500) (0.500 - x) = 4.8x10-2
CHECK: 0.020/0.500 = 0.04 or 4% percent error
(x) (x)
(b) Kc = 8.3x10-4 =
(0.010 - x)
Dropping the -x will give a value for x = 2.9x10-3M. (0.010 - x) 0.0071M
68
Strategy
69
Solution
KP = Kc(0.0821T )n
70
Check
71
The reaction quotient (Qc) is calculated by substituting the
initial concentrations of the reactants and products into the
equilibrium constant (Kc) expression.
IF
Qc < Kc system proceeds from left to right to reach equilibrium
Qc = Kc the system is at equilibrium
Qc > Kc system proceeds from right to left to reach equilibrium
72
At the start of a reaction, there are 0.249 mol N2, 3.21 x 10-2
mol H2, and 6.42 x 10-4 mol NH3 in a 3.50-L reaction vessel at
375C. If the equilibrium constant (Kc) for the reaction
73
Solution
0.249 mol
[N 2 ]o = = 0.0711 M
3.50 L
3.21 10 2 mol
[H 2 ]o = = 9.17 103 M
3.50 L
6.42 104 mol
[NH3 ]o = = 1.83 10 4 M
3.50 L
74
Next we write
75
A mixture of 0.500 mol H2 and 0.500 mol I2 was placed in a
1.00-L stainless-steel flask at 430C. The equilibrium constant
Kc for the reaction H2(g) + I2(g) 2HI(g) is 54.3 at this
temperature. Calculate the concentrations of H2, I2, and HI at
equilibrium.
76
Solution We follow the preceding procedure to calculate the
equilibrium concentrations.
[HI]2
Kc =
[H 2 ][I 2 ]
Substituting, we get
(2x) 2
54.3 =
(0.500 - x)(0.500 - x)
2x
7.37 =
0.500 - x
x = 0.393 M
78
Step 3: At equilibrium, the concentrations are
79
For the same reaction and temperature as in Example 15.6,
H2(g) + I2(g) 2HI(g), suppose that the initial concentrations
of H2, I2, and HI are 0.00623 M, 0.00414 M, and 0.0224 M,
respectively. Calculate the concentrations of these species at
equilibrium.
80
Strategy
81
Solution
[HI]02 (0.0224)2
Qc = = = 19.5
[H 2 ]0 [I 2 ]0 (0.00623)(0.00414)
82
Step 1: Let x be the depletion in concentration (mol/L) of H2
and I2 at equilibrium. From the stoichiometry of the
reaction it follows that the increase in concentration for
HI must be 2x. Next we write
H2 + I2 2HI
Initial (M): 0.00623 0.00414 0.0224
Change (M): -x -x + 2x
Equilibrium (M): (0.00623 - x) (0.00414 - x) (0.0224 + 2x)
83
Step 2: The equilibrium constant is
[HI]2
Kc =
[H 2 ][I 2 ]
Substituting, we get
(0.0224 + 2x)2
54.3 =
(0.00623 - x)(0.00414 - x)
86
Check
87
LeChteliers Principle
If an external stress is applied to a system at equilibrium, the system
adjusts in such a way that the stress is partially offset as the system
reaches a new equilibrium position.
1. Changes in Concentration
Equilibrium
Add
shifts left to
NH3
offset stress
LeChteliers Principle
Changes in Concentration continued
Add
Remove Remove
Add
aA + bB cC + dD
colder hotter 91
Le Chteliers Principle
4. Adding a Catalyst
does not change K
does not shift the position of an equilibrium system
system will reach equilibrium sooner
93
LeChteliers Principle
Applications to real life:
1. Altitude sickness
hemoglobin + oxygen oxyhemoglobin
3. Carbonated beverages
CO2(g) + H2O(l) H2CO3(aq)
Consider the following equilibrium process between dinitrogen
tetrafluoride (N2F4) and nitrogen difluoride (NF2):
(a) What does the sign of H indicate about the heat change
(endothermic or exothermic) for the forward reaction?
(a) The stress applied is the heat added to the system. Note
that the N2F4 2NF2 reaction is an endothermic process
(H > 0), which absorbs heat from the surroundings.
Therefore, we can think of heat as a reactant
97
The equilibrium constant
[NF2 ]2
Kc =
[N 2 F4 ]
will therefore increase with increasing temperature because the
concentration of NF2 has increased and that of N2F4 has
decreased. Recall that the equilibrium constant is a constant
only at a particular temperature. If the temperature is changed,
then the equilibrium constant will also change.
(b) The stress here is the removal of N2F4 gas. The system will
shift to replace some of the N2F4 removed. Therefore, the
system shifts from right to left until equilibrium is reestablished.
As a result, some NF2 combines to form N2F4.
98
Comment
99
(c) The stress applied is a decrease in pressure (which is
accompanied by an increase in gas volume). The system
will adjust to remove the stress by increasing the pressure.
Recall that pressure is directly proportional to the number
of moles of a gas. In the balanced equation we see that
the formation of NF2 from N2F4 will increase the total
number of moles of gases and hence the pressure.
Therefore, the system will shift from left to right to
reestablish equilibrium. The equilibrium constant will
remain unchanged because temperature is held constant.
100
(d) The function of a catalyst is to increase the rate of a
reaction. If a catalyst is added to a reacting system not at
equilibrium, the system will reach equilibrium faster than
if left undisturbed. If a system is already at equilibrium, as
in this case, the addition of a catalyst will not affect either
the concentrations of NF2 and N2F4 or the equilibrium
constant.
101
Exercises
Where would the equilibrium shift to?
(Right, Left or Remain Unchanged)
N2 + 3 H2 2 NH3 + heat [Haber Process]
a. Add more H2
b. Add more NH3
c. INC Ptotal
d. INC Temp
Le Chteliers Principle
If an external stress is applied to a system at equilibrium, the
system adjusts in such a way that the stress is partially offset
as the system reaches a new equilibrium position.
Changes in Concentration
Equilibrium
Add
shifts left to
NH3
offset stress
103
At 720C, the equilibrium constant Kc for the reaction
104
Strategy
(a) What is the stress applied to the system? How does the
system adjust to offset the stress?
105
Solution
106
(b) At the instant when some of the NH3 is added, the system
is no longer at equilibrium. The reaction quotient is given by
[NH3 ]02
Qc =
[N 2 ]0 [H 2 ]30
(3.65) 2
(0.683)(8.80)3
= 2.86 102
107
Figure 15.7 shows qualitatively the changes in concentrations
of the reacting species.
108
Consider the following equilibrium systems:
109
Strategy
110
Solution
(a) Consider only the gaseous molecules. In the balanced
equation, there are 3 moles of gaseous reactants and 2
moles of gaseous products. Therefore, the net reaction will
shift toward the products (to the right) when the pressure is
increased.
112