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Concepts
Dynamic Equilibrium
Many reactions are reversible: this is to say that when
the reaction appears to be complete, amounts of both
reactant and product exist.
We show reversible reactions using a double arrow
or
The forward reaction is read left to right, while the
reverse reaction is read right to left.
aA + bB
cC + dD
In a Closed System
The overall quantities are fixed
Whether we started with all reactant or all product,
we will always have the same composition at
equilibrium under the same conditions
aA + bB
cC + dD
Stoichiometric coefficients (a,b,c,d) are the exponent for
each substance
Called the reaction quotient (Q) at any time,
Q
[C]c [D]d
[A]a [B]b
[Q
]Q
N
O
2
4
2
[[C
]N
O
2
H
3
2]
N2 + 3H2(g) 2NH3(g)
20
NH3
N2 H2
KP
2
PNH
3
PN 2 PH22
Kp vs Kc
If PV = nRT, then P/RT = n/V
Substituting P/RT for molar concentration into the mass
action expression, Kc, results in a pressure-based formula
ng = [moles of gas in product] [moles of gas in the reactant]
R = 0.0821 L atm mol-1 K-1
KP = Kc(RT)n
11
cn
K
pcn(RT)K
11.7 = Kc
12
0.99
2.0
24
2400
None of these
13
Kp vs Kx (mole fraction)
aA + bB
cC + dD
Heterogeneous Equilibria
15
Kc
16
[Ca 3 (PO 4 ) 2 ]
[Ca 2+ ]3 [PO 43 ]2
B.
Q
1
[Ca 3 (PO 4 ) 2 ]
C.
Q
2+ 3
3 2
[Ca ] [PO4 ]
1
D.
Q
2+ 3
3 2
[Ca ] [PO 4 ]
18
19
Equilibrium Positions
Equilibrium positions are a combination of
concentrations that allow Q = K
There are an infinite number of possible
equilibrium positions
20
Equilibrium Shifts
Le Chteliers principle - a system at equilibrium
(Q = K) when upset by a disturbance that causes
(Q K) will shift to offset the stress
A shift to the right is when the forward reaction is
dominant (Q < K)
A shift to the left is when the reverse direction is
dominant (Q > K)
21
22
23
24
Initially, Q = K
[NH3] is inverse to Q
NH3(aq) is added
Q
Cu(H 2 O)6 2+ NH 3
Initially, Q = K
[Cu2+] is inverse to Q
increasing [Cu2+] decreases Q
Q < K shifts right
25
NH3
Q
3
N2 H2
In the reaction:
H3PO4(aq) + 3OH-(aq) 3H2O(l) + PO43-(aq)
What will happen if PO43- is removed?
Q is proportional to the [PO43-]
Decreasing [PO43-] decreases Q
Q < K shifts right
Q
PO4
OH
H3 PO 4
27
Temperature Effects
The product efficiency of the reaction depends on
the temperature, and whether the reaction is
endothermic or exothermic
Write mass action expression with heat term as if
it were a concentration and predict shifts as before
Figure 14.6 The effect of temperature on the
equilibrium Cu(H2O)42++ 4Cl
CuCl42 + 4H2O.
In the center, an equilibrium mixture of the two
complexes. When the solution is cooled in ice (left),
the equilibrium shifts toward the blue Cu(H2O)42+.
When heated in boiling water (right), the equilibrium
shifts toward CuCl42-. This behavior indicates that the
reaction is endothermic in the forward direction.
28
Learning Check
3
[Q
P
O
]
4
H
-4
heat
The reaction
H3PO4(aq) + 3OH-(aq) 3H2O(l) + PO43-(aq) is
exothermic. What will happen if the system is cooled?
30
Q
H
C
c0.2719
3O
2O
4K
2H
Learning Check:
In the reaction
H2C2O4(g) + H2O(l) H3O+(aq) + HC2O4-(aq),
31
2
2
N
O
2
3
1
K
4
.
8
1
0
c
O
33
34
QKshiftrgh2.0-x
2
D
Q
B
A
2
2
.Q
5
0
5
.
0
2
x
2
6.251
0,
For the reaction A + B 2D, K = 10,000, what are the
equilibrium concentrations if we start with 2.0 M A, 2.0 M B,
and 5.0 M D?
I (M) 2.0
C (M) -x
E (M) 2.0 - x
2 .0
-x
2.0 - x
2D
5.0
+ 2x
5.0 + 2x
x = 1.91
35
ln K
RT
18.9 Equilibrium constants can be estimated from standard free energy changes
36
Learning Check
Determine the value of K at 298 K and 500 K
CaCO3(s) CO2(g) + CaO(s)
Hrxn = 178 kJ
CaCO3
CO2
CaO
K = e(-G/RT)
K298 = e(-130.2/(0.008314 298))
Hf
1207
393.5 635.5
Sf
92.9
213.6
= 1.5 10-23
K500 = 6.06 10-11
Gf,298 1128.8
40
394.4 604.2
18.9 Equilibrium constants can be estimated from standard free energy changes
37
Learning Check
Determine the Value of K at 298 K and 500 K
2C6H6(l) + 15O2(g) 12CO2(g) + 6H2O(g)
G = H- TS = -RT ln K; K = e(G/RT)
K298 = e(+7146.6/(0.008314 298))
= e2884 huge!
K500 = e1862
Hrxn = -6285.8 kJ
Srxn = 3128.8 J/K
G298 = -6368 kJ
G500 = -7850.2 kJ
C6H6
O2
CO2
H2O
Hf
+49.0
393.5
241.8
Sf
173.3
205.0
213.6
188.7
Gf298
+124.3
394.4
228.6
18.9 Equilibrium constants can be estimated from standard free energy changes
38
Your Turn!
Given that H = -97.3 kJ , S = -122.1 J mol-1 K-1, the
pressure of HCl is 2 atm, and that of H2O is 1.0 atm, What is
the value of K at 500. K?
MgO(s) + 2HCl(g) H2O(g) + MgCl2(s)
A. 0.99
G = -97.3 - (500 -0.1221)
B. 1.01
C. 8.20
-36.25 kJ
D. 0.27
E. None of these -(-36.54/(0.008314 500))
6.11 103
18.9 Equilibrium constants can be estimated from standard free energy changes
39
N
O
p
2
4
K
p
x
1
6
3
.
5
1
0
2
0
.
2
0
Q
0
2
K.s2hiftrgh
For the reaction 2A(g) B(g) given that the Kp = 3.5 10-16
at 25 C, and we place 0.2 atm A into the container, what will
be the pressure of B at equilibrium?
2A
B
I
C
E
0.2
-2x
0.2 - 2x
0.2
0 atm
+x
x
x = 1.4 10-17
0.3 M
0.002 M
0.04 M
0.5 M
42