Chemeqb

Chapter 6
Chemical Equilibrium
Chemistry: The Molecular Nature

of Matter, 6E
Jespersen/Brady/Hyslop
Dynamic Equilibrium in Chemical
Systems
Chemical equilibrium exists when
Rates of forward and reverse reactions are equal
Reaction appears to stop
[reactants] and [products] don't change over
time
Remain constant
Both forward and reverse reaction never cease
Equilibrium signified by double arrows ( )
or equal sign (=)
Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 2

Dynamic Equilibrium
N2O4 2 NO2
Initially forward reaction rapid
As some reacts [N2O4] so rate forward
Initially Reverse reaction slow
No products
As NO2 forms
Reverse rate
Ions collide more frequently as [ions]
Eventually rateforward = ratereverse
Equilibrium
Dynamic Equilibrium
(Fig. 15.1)
Almost all systems come to equilibrium

Where equilibrium lies depends on system
Some systems equilibrium hard to detect
Essentially no reactants or no products present
Reaction Reversibility
Closed system
Equilibrium can be
reached from either
direction
Independent of whether
it starts with reactants
or products
Always have the same
composition at
equilibrium under same
conditions N 2O 4 2 NO2
Reactants Equilibrium Products
N2O4 2 NO2
For given overall system composition
Always reach same equilibrium concentrations
Whether equilibrium is approached from forward or
reverse direction
Equilibrium
Simple relationship among [reactants] and
[products] for any chemical system at
equilibrium
Called = mass action expression
Derived from thermodynamics
Forward reaction: A B Rate = kf[A]
kf
k
Reverse reaction: A B Rate = kr[B]
r
At equilibrium: A B kf[A] = kr[B]

rate forward = rate reverse
rearranging: [B] k f
constant
[A] k r
Ex: H2(g) + I2(g) 2HI(g) 440C
Expt Initial Equilm Equilm
# Amts Amts [M]
I 1.00 mol H2 0.222 mol H2 0.0222 M H2
10 L 1.00 mol I2 0.222 mol I2 0.0222 M I2
0.00 mol HI 1.56 mol HI 0.156 M HI
II 0.00 mol H2 0.350 mol H2 0.0350 M H2
10 L 0.100 mol I2 0.450 mol I2 0.0450 M I2
3.50 mol HI 2.80 mol HI 0.280 M HI

Ex: H2(g) + I2(g) 2HI(g) 440C
Expt Initial Amts Equilm Equilm
# Amts [M]
III 0.0150 mol H2 0.150 mol H2 0.0150 M H2
10 L 0.00 mol I2 0.135 mol I2 0.0135 M I2
1.27 mol HI 1.00 mol HI 0.100 M HI
IV 0.00 mol H2 0.442 mol H2 0.0442 M H2
10 L 0.00 mol I2 0.442 mol I2 0.0442 M I2
4.00 mol HI 3.11 mol HI 0.311 M HI

Mass Action Expression (MAE)
Uses stoichiometric coefficients as exponent
for each reactant
For reaction: aA + bB cC + dD
c d
[C] [D]
Q a b
[A] [B]
Reaction quotient
Numerical value of mass action expression
Equals Q at any time, and
Equals K only when reaction is known to be at
equilibrium
Mass Action Expression
2
[HI]
Q = same for all data sets at equilibrium
[H2 ][I 2 ]
Equilibrium Concentrations
(M) [HI]2
Q
Expt [H2] [I2] [HI] [H2 ][I 2 ]
I 0.0222 0.0222 0.156 (0.156 )2
49.4
(0.0222 )(0.0222 )
(0.280 )2
II 0.0350 0.0450 0.280 (0.0350 )(0.0450 )
49.8
(0.100 )2
III 0.0150 0.0135 0.100 (0.0150 )(0.0135 )
49.4
(0.311)2
IV 0.0442 0.0442 0.311 (0.0442 )(0.0442 )
49.5
Average = 49.5
Equilibrium Law
For reaction at equilibrium write the following
Equilibrium Law (at 440 C)
2
[HI]
Kc 49.5
[H2 ][I 2 ]
Equilibrium constant = Kc = constant at given T
Use Kc since usually working with concentrations in
mol/L
For chemical equilibrium to exist in reaction
mixture, reaction quotient Q must be equal to
equilibrium constant, Kc

Predicting Equilibrium Law
For general chemical reaction:
dD + eE fF + gG
Where D, E, F, and G represent chemical formulas
d, e, f, and g are coefficients
f g
[F] [G]
Mass action expression =
[D]d [E]e
Note: Exponents in mass action expression
are stoichiometric coefficients in balanced
equation. [F] f [G]g
Equilibrium law is: K c
[D]d [E]e
Ex. Equilibrium Law
3 H2(g) + N2(g) 2 NH3(g)
Kc = 4.26 x 108 at 25 C
What is equilibrium law?
2
[NH3 ] 8
Kc 3
4.26 10
[H2 ] [N2 ]

Learning Check
Write mass action expressions for the following:
2 NO2 (g) N2O4 (g)
[N2O4]
Q 2
[NO2]
2CO (g) + O2 (g) 2 CO2 (g)

2
[CO2]
Q 2
[CO] [O2]
Your Turn!
Which of the following is the correct mass
action expression (MAE) for the reaction:
Cu2+(aq) + 4NH3(aq) [Cu(NH3)42+](aq)?
[Cu(NH3 ) 24 ]
A. Q
[Cu2 ][NH3 ]4
[Cu(NH3 ) 24 ]
B. Q
[Cu2 ][NH3 ]
2 4
[Cu ][NH3 ]
C. Q
[Cu(NH3 ) 24 ]
D. none of these
Manipulating Equations for Chemical
Equilibria
Various operations can be performed on
equilibrium expressions
1. When direction of equation is reversed,
new equilibrium constant is reciprocal of
original
[C][D]
A+B C+D Kc
[A][B]
[A][B] 1
C +D A+B K c
[C][D] K c
Ex. Manipulating Equilibria 1
1. When direction of equation is reversed, new
equilibrium constant is reciprocal of original
3 H2(g) + N2(g) 2 NH3(g) at 25C

2
[NH3 ] 8
Kc 4.26 10
[H2 ]3 [N2 ]
2 NH3(g) 3 H2(g) + N2(g) at 25C
3
[H2 ] [N 2 ] 1 1 9
K c 2.35 10
[NH3 ] 2 Kc 4.26 10 8

Manipulating Equilibria 2
2. When coefficients in equation are
multiplied by a factor, equilibrium
constant is raised to a power equal to that
factor.
[C][D]
A+B C+D Kc
[A][B]
3A + 3B 3C + 3D
3 3
[C] [D] [C][D] [C][D] [C][D] 3
K c Kc
[A]3 [B] 3 [A][B] [A][B] [A][B]
2. When coefficients in equation are multiplied by
factor, equilibrium constant is raised to power
equal to that factor
3 H2(g) + N2(g) 2 NH3(g) at 25C
2
[NH3 ]
Kc 4.26 10 8
[H2 ]3 [N2 ]
multiply by 3
9 H2(g) + 3 N2(g) 6 NH3(g)
[NH3 ]6 3
K c 9 3
Kc
[H2 ] [N2 ]
3. When chemical equilibria are added,
their equilibrium constants are
multiplied
[C ][D ]
A+B C + D Kc
1
[A ][B ]
C+E F+G [F ][G ]
K c2
[C ][E ]
A+B+E D+F+G
[C ][D ] [F ][G ] [D ][F ][G ]
K c3 K c1 K c 2
[A ][B ] [C ][E ] [A ][B ][E ]
3. When chemical equilibria are added, their
equilibrium constants are multiplied
2 NO2(g) NO3(g) + NO(g) [NO][NO3 ]
K c1
[NO 2 ]2
NO3(g) + CO(g) NO2(g) + CO2(g) [NO2 ][CO 2 ]
K c2
[NO3 ][CO]
NO2(g) + CO(g) NO(g) + CO2(g) [NO][CO2 ]
K c3
[NO 2 ][CO]
[NO][NO3 ] [NO 2 ][CO 2 ] [NO][CO2 ]

[NO 2 ]2 [NO 3 ][CO] [NO2 ][CO]
Therefore K c1 K c 2 K c 3
Learning Check
For: N2(g) + 3 H2(g) 2 NH3(g)
Kc = 500 at a particular temperature.
What would be Kc for following?
2 NH3(g) N2(g) + 3 H2(g)
1 1
K c 0.002
Kc 500
N2(g) + 3/2 H2(g) NH3(g)
12
K c K c 500 22.4

Equilibrium Constant, Kc
Constant value equal to ratio of product
concentrations to reactant concentrations
raised to their respective exponents
[products]f
Kc d
[reactants ]
Changes with temperature (vant Hoff
Equation)
Depends on solution concentrations
Assumes reactants and products are in
solution
Equilibrium Constant, Kp
Based on reactions in which substances are
gaseous
Assumes gas quantities are expressed in
atmospheres in mass action expression
Use partial pressures for each gas in place of
concentrations
Ex. N2 (g) + 3 H2 (g) 2 NH3 (g)
2
PNH
KP 3
PN2 PH3
2
How are Kp and Kc Related?
Start with Ideal Gas Law
PV=nRT
Rearranging gives
n
P RT MRT
V
Substituting P/RT for molar concentration
into Kc results in pressure-based formula
n = moles of gas in product moles of
gas in reactant
Kp Kc (RT )n
Learning Check
Consider the reaction: 2NO2(g) N2O4(g)
If Kp = 0.480 for the reaction at 25C, what is
value of Kc at same temperature?
n = nproducts nreactants = 1 2 = 1
n
Kp Kc(RT)
Kp 0.480
Kc
n 1
(RT) (0.0821 298K )
Kc = 11.7
Your Turn!
Consider the reaction A(g) + 2B(g) 4C(g)
If the Kc for the reaction is 0.99 at 25C, what
would be the Kp?
A. 0.99
B. 2.0 n=(4 3)=1
C. 24. Kp = Kc(RT)n
D. 2400 Kp= 0.99*(0.082057*298.15)1
E. None of these Kp = 24

Homogeneous reaction/equilibrium
All reactants and products in same phase
Can mix freely
Heterogeneous reaction/equilibrium
Reactants and products in different phases
Cant mix freely
Solutions are expressed in M
Gases are expressed in M
Governed by Kc

Heterogeneous Equilibria
2NaHCO3(s) Na2CO3(s) + H2O(g) + CO2(g)
Equilibrium Law = [Na 2CO 3 (s )][H 2O ( g )][CO 2 ( g )]
K
[NaHCO 3 (s )]2
Can write in simpler form
For any pure liquid or solid, ratio of moles to
volume of substance (M) is constant
Ex. 1 mol NaHCO3 occupies 38.9 cm3
2 mol NaHCO3 occupies 77.8 cm3
2 mol NaHCO3
M 25.7M
0.0778 L
1 mol NaHCO3
M 25.7M
0.0389 L
Heterogeneous Equilibria
2NaHCO3(s) Na2CO3(s) + H2O(g) + CO2(g)
Ratio (n/V) or M of NaHCO3 is constant (25.7 mol/L)
regardless of sample size
Likewise can show that molar concentration of
Na2CO3 solid is constant regardless of sample size
So concentrations of pure solids and liquids
can be incorporated into equilibrium constant,
Kc [Na2 CO3 (s )]
Kc K 2
[H2 O( g )][CO2 ( g )]
[NaHCO3 (s )]
Equilibrium law for heterogeneous system written
without concentrations of pure solids or liquids
Interpreting KC
Large K (K>>1)
Means product rich mixture
Reaction goes far toward
completion
Ex.
2SO2(g) + O2(g) 2SO3(g)
Kc = 7.0 1025 at 25 C
2 25
[SO 3 ] 7.0 10
Kc
2

[SO 2 ] [O 2 ] 1
Interpreting KC
Small K (K<<1)
Means reactant rich
mixture
Only very small amounts of
product formed
Ex.
H2(g) + Br2(g) 2HBr(g)
Kc = 1.4 1021 at 25 C
2 21
[HBr] 1.4 10
Kc
[H2 ][Br2 ] 1
Interpreting KC
K 1
Means product and
reactant concentrations
close to equal
Reaction goes only ~
halfway

Size of K gives measure of how
reaction proceeds
K >> 1 [products] >> [reactants]

K=1 [products] = [reactants]
K << 1 [products] << [reactants]
Learning Check
Consider the reaction of 2NO2(g) N2O4(g)
If Kp = 0.480 at 25C, does the reaction favor
product or reactant?
K is small (K < 1)
Reaction favors reactant
Since K is close to 1, significant amounts of
both reactant and product are present
Equilibrium Positions and Shifts
Equilibrium positions
Combination of concentrations that allow Q = K
Infinite number of possible equilibrium positions
Le Chteliers principle
System at equilibrium (Q = K) when upset by
disturbance (Q K) will shift to offset stress
System said to shift to right when
forward reaction is dominant (Q < K)
System said to shift to left when reverse
direction is dominant (Q > K)

Relationship Between Q and K
Q=K reaction at equilibrium
Q<K reactants products
Too many reactants

Must convert some reactant to product to move
reaction toward equilibrium
Q>K reactants products
Too many products
Must convert some product to reactant to move
reaction toward equilibrium

Examples of Le Chteliers Principle
Lets see how this works with changes in
1. Concentration
2. Pressure and volume
3. Temperature
4. Catalysts
5. Adding inert gas to system at constant
volume

Effect of Change in Concentration
2SO2(g) + O2(g) 2SO3(g)
Kc = 2.4 x 10-3 at 700 oC
Which direction will the reaction move if
0.125 moles of O2 is added to an equilibrium
mixture ?
A. Towards the products
B. Towards the reactants
C. No change will occur

Effect of Change in Concentration
When changing concentrations of reactants
or products
Equilibrium shifts to remove reactants or
products that have been added
Equilibrium shifts to replace reactants or
products that have been removed

Effect of Pressure and Volume Changes
Consider gaseous system at constant T and n
3H2(g) + N2(g) 2NH3(g) 2
PNH
If reduce volume (V) K P 3
PN2 PH3
Expect Pressure to increase (P) 2
To reduce pressure, look at each side of reaction

Which has less moles of gas
Reactants = 3 + 1 = 4 moles gas
Products = 2 moles gas
Reaction favors products (shifts to right)

Effect of P and V Changes
Consider gaseous system at constant T and n
Ex. H2(g) + I2(g) 2 HI(g)
2
PHI
KP
PH2 PI2
If pressure is increased, what is the effect on
equilibrium?
nreactant = 1 + 1 = 2
nproduct = 2
Predict no change or shift in equilibrium

2NaHSO3(s) NaSO3(s) + H2O(g) + SO2(g)
K P PH2OPSO2
If you decrease volume of reaction, what is
the effect on equilibrium?
Reactants: no moles gas = all solids
Products: 2 moles gas
V, causes P
Reaction shifts to left (reactants), as this has
fewer moles of gas
Reducing volume of gaseous reaction
mixture causes reaction to decrease number
of molecules of gas, if it can
Increasing pressure
Moderate pressure changes have negligible
effect on reactions involving only liquids
and/or solids
Substances are already almost incompressible
Changes in V, P and [X] effect position of
equilibrium (Q), but not K
Effect of Temperature Changes
H2O(s) H2O() H =+6 kJ (at 0 C)
Energy + H2O(s) H2O()
Energy is reactant
Add heat, shift reaction right
3H2(g) + N2(g) 2NH3(g) Hf= 47.19 kJ
3 H2(g) + N2(g) 2 NH3(g) + energy
Energy is product
Add heat, shift reaction left

Effect of Temperature Changes
T shifts reaction in direction that produces
endothermic (heat absorbing) change
T shifts reaction in direction that produces
exothermic (heat releasing) change
Changes in T change value of mass action
expression at equilibrium, so K changed
K depends on T
T of exothermic reaction makes K smaller
More heat (product) forces equilibrium to reactants
T of endothermic reaction makes K larger
More heat (reactant) forces equilibrium to products
Catalysts And Equilibrium
Catalyst lowers Ea
for both forward
and reverse
reaction
Change in Ea
affects rates kr
and kf equally
Catalysts have no
effect on
equilibrium
Effect of Adding Inert Gas
Inert gas
One that does not react with components of
reaction
Ex. Argon, Helium, Neon, usually N2
Adding inert gas to reaction at fixed V (n and
T), P of all reactants and products
Since it doesnt react with anything
No change in concentrations of reactants or
products
No net effect on reaction

Your Turn!
The following are equilibrium constants for the
reaction of acids in water, Ka. Which is the
most efficient reaction?
A. Ka = 2.2103
B. Ka = 1.8105
C. Ka = 4.01010
D. Ka = 6.3103

Equilibrium Calculations
For gaseous reactions, use either KP or KC
For solution reactions, must use KC
Either way, two basic categories of
calculations
1. Calculate K from known equilibrium
concentrations or partial pressures
2. Calculate one or more equilibrium
concentrations or partial pressures using
known KP or KC

Calculating KC from Equilibrium
Concentrations
When all concentrations at equilibrium are
known
Use mass action expression to relate
concentrations to KC
Two common types of calculations
A. Given equilibrium concentrations, calculate K
B. Given initial concentrations and one final
concentration
Calculate equilibrium concentration of
all other species
Then calculate K
Calculating KC Given Equilibrium
Concentrations
Ex. 1 N2O4(g) 2NO2(g)
If you place 0.0350 mol N2O4 in 1 L flask at
equilibrium, what is KC?
[N2O4]eq = 0.0292 M
[NO2]eq = 0.0116 M
2 2
[NO 2 ] [0.0116]
Kc Kc
[N 2O 4 ] [0.0292]
KC = 4.61 103
Your Turn!
For the reaction: 2A(aq) + B(aq) 3C(aq)
the equilibrium concentrations are: A = 2.0 M,
B = 1.0 M and C = 3.0 M. What is the
expected value of Kc at this temperature?
A. 14 [C]3
Kc
B. 0.15 2
[A] [B]
C. 1.5
[3.0]3
D. 6.75 Kc 2
[2.0] [1.0]

Calculating KC Given Initial Concentrations
and One Final Concentration
Ex. 2 2SO2(g) + O2(g) 2SO3(g)
1.000 mol SO2 and 1.000 mol O2 are placed in
a 1.000 L flask at 1000 K. At equilibrium
0.925 mol SO3 has formed. Calculate KC for
this reaction.
1st calculate concentrations of each
Initial 1.00mol
[SO 2 ] [O 2 ] 1.00M
1.00L
Equilibrium
0.925mol
[SO 3 ] 0.925M
1.00L
How to Solve:
Set up Concentration Table
Based on the following:
Changes in concentration must be in same ratio
as coefficients of balanced equation
Set up table under balanced chemical equation
Initial concentrations
Controlled by person running experiment
Changes in concentrations
Controlled by stoichiometry of reaction
Equilibrium concentrations
Equilibrium Initial Change in
=
Concentration Concentration Concentration
Next Set up Concentration Table
2SO2(g) + O2(g) 2SO3(g)
Initial Conc. (M) 1.000 1.000 0.000
Changes in Conc. (M) 0.925 0.462 +0.925
Equilibrium Conc. (M) 0.075 0.538 0.925
[SO2] consumed = Amt of SO3 formed
= [SO3] at equilibrium = 0.925 M
[O2] consumed = amt SO3 formed
= 0.925/2 = 0.462 M
[SO2] at equilibrium = 1.000 0.975 = 0.075
[O2] at equilibrium = 1.00 0.462 = 0.538 M
Ex. 2
Finally calculate KC at 1000 K
[SO 3 ]2
Kc
[SO 2 ]2 [O 2 ]
2
[0.925]
Kc 2
[0.075] [0.538]
Kc = 2.8 102 = 280

Summary of Concentration Table
Used for most equilibrium calculations (Ch
15, 17, and 18)
1. Equilibrium concentrations are only values
used in mass action expression
Values in last row of table
2. Initial value in table must be in units of
mol/L (M)
[X]initial = those present when reaction
prepared
No reaction occurs until everything is
mixed
Summary of Concentration Table
3. Changes in concentrations always occur in
same ratio as coefficients in balanced
equation
4. In change row be sure all [reactants]
change in same directions and all [products]
change in opposite direction.
If [reactant]initial = 0, its change must be + ()
because [reactant]final negative
If [reactants] , all entries for reactants in change
row should have minus sign and all entries for
products should be positive

Calculate [X]equilibrium from Kc and [X]initial
When all concentrations but one are known
Use mass action expression to relate Kc
and known concentrations to obtain
missing concentrations
Ex. 3 CH4(g) + H2O(g) CO(g) + 3H2(g)
At 1500 C, Kc = 5.67. An equilibrium
mixture of gases had the following
concentrations: [CH4] = 0.400 M and
[H2] = 0.800M and [CO] =0.300M.
What is [H2O] at equilibrium ?

Calculate [X]equilibrium from Kc and [X]initial
Ex. 3 CH4(g) + H2O(g) CO(g) + 3H2(g) Kc = 5.67
[CH4] = 0.400 M; [H2] = 0.800M; [CO] =0.300M
What is [H2O] at equilibrium?
First, set up equilibrium
3
[CO][H2 ] [CO][H2 ]3
Kc [H2O]
[CH4 ][H2O] [CH4 ]K c
Next, plug in equilibrium concentrations and Kc
[0.300][0. 800]3 0.154
[H2O]
[0.400](5.67) 2.27
[H2O] = 0.0678 M
Calculating [X]Equilibrium from Kc
When Initial Concentrations Are Given
Write equilibrium law/mass action expression
Set up Concentration table
Allow reaction to proceed as expected,
using x to represent change in
concentration
Substitute equilibrium terms from table into
mass action expression and solve

Calculate [X]equilibrium from [X]initial and KC
Ex. 4 H2(g) + I2(g) 2HI(g) at 425 C

KC = 55.64
If one mole each of H2 and I2 are placed in a
0.500 L flask at 425 C, what are the
equilibrium concentrations of H2, I2 and HI?
Step 1. Write Equilibrium Law
2
[HI ]
Kc 55.64
[H 2 ][I 2 ]

Ex. 4 Step 2. Concentration Table
Conc (M) H2(g) + I2(g) 2HI (g)
Initial 2.00 2.00 0.000
Change x x +2x
Equilm 2.00 x 2.00 x +2x
Initial [H2] = [I2] = 1.00 mol/0.500L =2.00M
Amt of H2 consumed = Amt of I2 consumed = x
Amt of HI formed = 2x
(2x ) 2 (2x ) 2
55.64
(2.00 x )(2.00 x ) (2.00 x ) 2

Ex. 4 Step 3. Solve for x
Both sides are squared so we can take
square root of both sides to simplify
(2x ) 2
K 55.64 2
(2.00 x )
2x
7.459 7.459(2.00 x ) 2x
(2.00 x )
14.918 7.459x 2x 14.918 9.459x
14.918
x 1.58
9.459
Ex. 4 Step 4. Equilibrium Concentrations

Initial 2.00 2.00 0.00
Change 1.58 1.58 +3.16
Equilm 0.42 0.42 +3.16
[H2]equil = [I2]equil = 2.00 1.58 = 0.42 M

[HI]equil = 2x = 2(1.58) = 3.16

Ex. 5 H2(g) + I2(g) 2HI(g) at 425 C

KC = 55.64
If one mole each of H2, I2 and HI are placed
in a 0.500 L flask at 425 C, what are the
equilibrium concentrations of H2, I2 and HI?
Now have product as well as reactants initially
2
[HI ]
Kc 55.64
[H 2 ][I 2 ]
Initial 2.00 2.00 2.00
Change x x +2x
Equilm 2.00 x 2.00 x 2.00 + 2x
(2.00 2x ) 2 (2.00 2x ) 2
55.64
(2.00 x )(2.00 x ) (2.00 x ) 2
(2.00 2x ) 2
K 55.64
(2.00 x ) 2

2.00 2x
7.459
(2.00 x )
7.459(2.00 x ) 2.00 2x
14.918 7.459x 2.00 2x
12.918 9.459x [H2]equil = [I2]equil = 2.00 x =

2.00 1.37 = 0.63 M
12.918
x 1.37 [HI]equil = 2.00 + 2x
9.459
= 2.00 + 2(1.37)
= 2.00 + 2.74
= 4.74 M
Your Turn!
N2(g) + O2(g) 2NO(g)
Kc = 0.0123 at 3900 oC
If 0.25 moles of N2 and O2 are placed in a
250 mL container, what are the equilibrium
concentrations of all species ?
A. 0.0526 M, 0.947 M, 0.105 M
B. 0.947 M, 0.947 M, 0.105 M
C. 0.947 M 0.105 M, 0.0526 M
D. 0.105 M, 0.105 M, 0.947 M

Your Turn! - Solution
Conc (M) N2(g) +O2(g) 2NO (g)

Initial 1.00 1.00 0.00
Change x x + 2x
Equil 1.00 x 1.00 x + 2x
0.250 mol
[N2 ] [O2 ] 1.00M
0.250 L
(2x )2 2x
0.0123 0.0123
(1 x ) 2
1x
x 0.0526M [NO] = 2x = 0.105M
Ex. 6
CH3CO2H(aq) + C2H5OH(aq) CH3CO2C2H5(aq) +
acetic acid ethanol ethyl acetate H2O(l)
KC = 0.11
An aqueous solution of ethanol and acetic
acid, each with initial concentration of 0.810
M, is heated at 100 C. What are the
concentrations of acetic acid, ethanol and
ethyl acetate at equilibrium?

When KC is very small

Ex. 7 2H2O(g) 2H2(g) + O2(g)
At 1000 C, KC = 7.3 1018
If the initial H2O concentration is 0.100M,
what will the H2 concentration be at
equilibrium?
[H2 ]2 [O 2 ] 18
Kc 2
7.3 10
[H2 O]
Conc (M) 2H2O(g) 2H2(g) + O2(g)
Initial 0.100 0.00 0.00
Change 2x +2x +x
Equilm 0.100 2x +2x +x
18 (2x )2 x 4x 3
7.3 10 2

(0.100 2x ) (0.100 2x )2
Cubic equation tough to solve
Make approximation
KC very small, so x will be very small
Assume we can neglect x
must prove valid later
Assume (0.100 2x) 0.100
Conc (M) 2H2O (g) 2H2 (g) + O2 (g)
Initial 0.100 0.00 0.00
Change 2x +2x +x
Equilm 0.100 +2x +x
Now our equilibrium expression simplifies to
2 3
18 (2x ) x 4x
7.3 10
(0.100)2 0.010
4x 3 0.010(7.3 10 18 ) = 7.3 1020
20
7.3 10
x3 1.8 10 20
4
Now take cubic root
3 20 7
x 1.8 10 2.6 10
x is very small
0.100 2(2.6107) = 0.09999948
Which rounds to 0.100 (3 decimal places)
[H2] = 2x = 2(2.6107)
= 5.2107 M
Simplifications: When Can You
Ignore x in Binomial (Ci x)?
If equilibrium law gives very complicated
mathematical problems
And if K is small
Change to reach equilibrium (x term) is also small
Compare initial concentration Ci in binomial to
value of K Ci
400
K
Use proof to show that dropped x term was
sufficiently small
dropped x term ?
Ci 0.05
Learning Check
For the reaction 2A(g) B(g)
given that Kp = 3.51016 at 25C, and we place 0.2
atm A into the container, what will be the pressure of B
at equilibrium? PN2O4
2A B Q
2
PNO
I 0.2 0 atm
C 2x +x 16 x
3.5 10
2
E 0.2 2x 0.2 x (0.2 )
0 x = 1.410 17
Q 0
2
(0.2) [B]= 1.41017 M
Q K shifts right proof: 1.41017/0.2<0.05
Your Turn!
In the reaction shown, K = 1.8 105
HC2H3O2(aq) + H2O(l) H3O+(aq) + C2H3O2(aq)
If we start with 0.3M HC2H3O2, what will be the
equilibrium concentration of C2H3O2 ?
A. 0.3 M
B. 0.002 M
C. 0.04 M
D. 0.5 M

Calculating KC Given Initial Concentrations
and One Final Concentration
Ex. 2a
H2(g) + I2(g) 2HI(g) @ 450 C
Initially H2 and I2 concentrations are 0.200
mol each in 2.00L (= 0.100M); no HI is
present
At equilibrium, HI concentration is 0.160 M
Calculate KC
To do this we need to know 3 sets of
concentrations: initial, change and
equilibrium

Chemeqb

Diunggah oleh

Informasi Dokumen

Deskripsi Asli:

Judul Asli

Hak Cipta

Format Tersedia

Bagikan dokumen Ini

Bagikan atau Tanam Dokumen

Opsi Berbagi

Apakah menurut Anda dokumen ini bermanfaat?

Apakah konten ini tidak pantas?

Hak Cipta:

Format Tersedia

Chemeqb

Diunggah oleh

Hak Cipta:

Format Tersedia

Chapter 6

Chemistry: The Molecular Nature

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 2

Almost all systems come to equilibrium

At equilibrium: A B kf[A] = kr[B]

II 0.00 mol H2 0.350 mol H2 0.0350 M H2

10 L 0.100 mol I2 0.450 mol I2 0.0450 M I2

3.50 mol HI 2.80 mol HI 0.280 M HI

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 8

IV 0.00 mol H2 0.442 mol H2 0.0442 M H2

10 L 0.00 mol I2 0.442 mol I2 0.0442 M I2

4.00 mol HI 3.11 mol HI 0.311 M HI

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 12

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 14

2CO (g) + O2 (g) 2 CO2 (g)

3 H2(g) + N2(g) 2 NH3(g) at 25C

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 18

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 23

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 28

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 29

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 34

K >> 1 [products] >> [reactants]

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 37

Too many reactants

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 38

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 39

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 40

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 41

To reduce pressure, look at each side of reaction

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 42

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 43

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 46

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 49

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 50

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 51

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 54

Kc = 2.8 102 = 280

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 58

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 60

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 61

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 63

Ex. 4 H2(g) + I2(g) 2HI(g) at 425 C

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 64

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 65

Conc (M) H2(g) + I2(g) 2HI (g)

[H2]equil = [I2]equil = 2.00 1.58 = 0.42 M

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 67

Ex. 5 H2(g) + I2(g) 2HI(g) at 425 C

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 69

14.918 7.459x 2.00 2x

12.918 9.459x [H2]equil = [I2]equil = 2.00 x =

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 71

Conc (M) N2(g) +O2(g) 2NO (g)

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 73

When KC is very small

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 80

Anda mungkin juga menyukai