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C + D ( forward) A + B (reverse) S Initially there is only A and B so only the forward reaction is possible S As C and D build up, the reverse reaction speeds up while the forward reaction slows down. S Eventually the rates are equal
concentrations and activation energy. S The concentrations do not change at equilibrium. S or if the reaction is verrrry slooooow.
lC + mD PRODUCTSpower REACTANTSpower
[A]j[B]k
Playing with K
S If we write the reaction in reverse. S lC + mD
[C]l[D]m
Playing with K
S If we multiply the equation by a
constant S njA + nkB nlC + nmD S Then the equilibrium constant is [C]nl[D]nm SK = [A]nj[B]nk
=
([C]l[D]m)n
([A] j[B]k)n
Kn =
K is CONSTANT
S At any temperature. S Temperature affects rate. S The equilibrium concentrations dont
have to be the same, only K. S Equilibrium position is a set of concentrations at equilibrium. S There are an unlimited number.
Equilibrium Constant
One for each Temperature
Calculate K
S N2 + 3H2 S Initial S [N2]0 =1.000 M S [H2]0 =1.000 M S [NH3]0 =0 M
Calculate K
S N2 + 3H2 S Initial S [N2]0 = 0 M S [H2]0 = 0 M S [NH3]0 = 1.000 M
2SO3(g)
Kp =
(PSO3)2
(PSO2)2 (PO2)
S
K=
[SO3]2
2
K=
(PSO3/RT)2 (PSO2/RT)2(PO2/RT)
K=
(PSO3)2
(1/RT)2
(PSO2)2(PO2) (1/RT)3
S
(1/RT)2
General Equation
S jA + kB
lC + mD
(CA)j(CB)kx(RT)j+k
S Kp = K (RT)(l+m)-(j+k) = K (RT)n S
Homogeneous Equilibria
S So far every example dealt with
reactants and products where all were in the same phase. S We can use K in terms of either concentration or pressure. S Units depend on reaction.
Heterogeneous Equilibria
S If the reaction involves pure solids or
pure liquids the concentration of the solid or the liquid doesnt change. S As long as they are not used up we can leave them out of the equilibrium expression. S For example
For Example
S H2(g) + I2(s) S K = [HI]2
2HI(g)
[H2][I2]
S But the concentration of I2 does not
change.
S K[I2]= [HI]2 = K
[H ]
Write the equilibrium constant for the heterogeneous reaction 2NaHCO3 (s) A. Na 2 CO3 (s) + CO 2 (g) + H 2 O(g). D.
[ CO2 ] [ H 2O]
B. [ Na 2 CO3 ] PCO2 [ H 2 O ]
C. PCO2 PH2 O
E.
go to reach equilibrium S Calculated the same as the equilibrium constant, but for a system not at equilibrium
S Q = [Products]coefficient
[Reactants] coefficient
S Compare value to equilibrium constant
What Q tells us
S If Q<K &Not enough products &Shift to right S If Q>K &Too many products &Shift to left S If Q=K system is at equilibrium
Example
S for the reaction S 2NOCl(g)
2NO(g) + Cl2(g)
0.0010 mol NO(g) and 0.00010 mol Cl2 are mixed in 2.0 L flask. proceed to reach equilibrium?
one equilibrium concentration. S Use stoichiometry to figure out other concentrations and K. S Learn to create a table of initial and final conditions.
2SO3(g)
SO2, 1.50 mol of O2 and 3.00 mol of SO3 were placed in a 1.00 L flask. At equilibrium 3.50 mol of SO3 were found to be present. Calculate S The equilibrium concentrations of O2 and SO2, K and KP
2SO2(g) + O2(g)
2SO3(g)
and .350 mol SO3 were placed in a 1.000 L container. When the system reaches equilibrium 0.045 mol of O2 are present. S Calculate the final concentrations of SO2 and SO3 and K
approach to take. S First lets look at the case of a LARGE value of K ( >100). S Allows us to make simplifying assumptions.
Example
S H2(g) + I2(g) 2HI(g) S K = 7.1 x 102 at 25C S Calculate the equilibrium
formed. S Set up table of initial, final and change in concentrations. S Assumption since K is large- reaction will almost go to completion.
S Stoichiometry tells us I2 is LR, it will be
H2(g)
I2(g)
2 HI(g) 0M
H2(g) 1.56 M
2 HI(g) 0M
S Using to stoichiometry we can find S Change in H2 = X-0.232 M S Change in HI = -twice change in H2 S Change in HI = 0.464-2X
H2(g) I2(g) 2 HI(g) initial 1.56 M 0.232 M 0M change X-0.232 M X-0.232 M 0.464-2X final X
S Now we can determine the final
concentrations by adding.
H2(g) I2(g) initial 1.56 M 0.232 M change X-0.232 M X-0.232 M final 1.328+X X equilibrium expression
SK =
Why we chose X
(0.464-2X)2 = 7.1 x 102 (1.328+X)(X) S Since X is going to be small, we can ignore it in relation to 0.464 and 1.328 S So we can rewrite the equation S 7.1 x 102 = (0.464)2
SK =
H2(g) I2(g) initial 1.56 M 0.232 M change X-0.232 M X-0.232 M final 1.328+X X
2.3 x 10-4 M
S H2 = 1.328 M S HI = 0.464 M
X is less than 5% of all the smallest concentrations, our assumption was valid. S If not we would have had to use the quadratic equation S More on this later. S Our assumption was valid.
Practice
S For the reaction Cl2 + O2
2ClO(g)
K = 156 S In an experiment 0.100 mol ClO, 1.00 mol O2 and 0.0100 mol Cl2 are mixed in a 4.00 L flask. S If the reaction is not at equilibrium, which way will it shift? S Calculate the equilibrium concentrations.
final concentrations. S Choose X to be small. S For this case it will be a product. S For a small K the product concentration is small.
For example
S For the reaction
2NOCl
2NO +Cl2
[NOCl]2
(1.20)2
2NOCl
Initial Change Final
S Choose X to be small S NO will be LR S Choose NO to be X
2NO +
0.45
Cl2
0.87
1.20
2NOCl
Initial Change Final 1.20
2NO +
0.45
Cl2
0.87
2NOCl
Initial Change Final
S Use stoichiometry
2NO +
0.45 X-.45 X
Cl2
0.87
1.20
S Now figure out the other changes S Change in Cl2 is 1/2 change in NO S Change in NOCl is - change in NO
2NOCl
Initial Change Final
q Now
2NO +
0.45
Cl2
0.87
1.20 0.45-X
2NOCl
Initial Change Final
q Now qK
2NO +
0.45
Cl2
0.87
= (X)2(0.5X+0.645) (1.65-X)2 q Now we can test our assumption X is small ignore it in + and -
2NOCl
Initial Change Final
qK
2NO +
0.45
Cl2
0.87
= (X)2(0.645) (1.65)2
= 1.6 x 10-5
2NOCl
Initial Change Final
q [NOCl] q [Cl
2]
2NO +
0.45
Cl2
0.87
= 1.64
= 0.649
q Check
Practice Problem
S For the reaction
2ClO(g)
Type 3 Mid-range Ks
.01<K<10
No Simplification
S Choose X to be small. S Cant simplify so we will have to solve
K=38.6
if 1.800 mol H2, 1.600 mol I2 and 2.600 mol HI are mixed in a 2.000 L container?
2NO2(g)
KP = .131 atm. What are the equilibrium pressures if a flask initially contains 1.000 atm N2O4?
Le Chteliers Principle
S If a stress is applied to a system at
equilibrium, the position of the equilibrium will shift to reduce the stress. S 3 Types of stress `Concentration `Pressure `Temperature
Change Pressure
S By changing volume S System will move in the direction that
has the least moles of gas. S Because partial pressures (and concentrations) change, a new equilibrium must be reached. S System tries to minimize the moles of gas if volume is reduced S And visa versa
Change in Pressure
S By adding an inert gas S Partial pressures of reactants and
Change in Temperature
S Affects the rates of both the forward
and reverse reactions. S Doesnt just change the equilibrium position, changes the equilibrium constant. S The direction of the shift depends on whether it is exo- or endothermic
Exothermic
S H<0 S Releases heat S Think of heat as a product S Raising temperature push toward
Endothermic
S H>0 S Produces heat S Think of heat as a reactant S Raising temperature push toward