chemical equilibrium - pbworks
TRANSCRIPT
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Chemical Equilibrium
The Concept of Equilibrium
Chemical equilibrium occurs when a reaction and its reverse reaction proceed at the same rate.
Chemical EquilibriumChemical equilibrium occurs when a reaction and its
reverse reaction proceed at the same rate.
N2O4 is a colorless gas. It decomposes into NO2, a browncolored gas.
Eventually, the forward and backward reactions reach a state of equilibrium.
This means that the colorless gas is decomposing at the same rate at which the brown gas is combining.
N2O4(g) 2NO2(g)
When both the forward and reverse reactions are being carried out, we write the equation with a double arrow.
Chemical Equilibrium
N2O4(g) 2NO2(g)
The Concept of Equilibrium
• As a system approaches equilibrium, both the forward and reverse reactions are occurring.
• When a reaction begins, the forward reaction occurs quickly, at first then begins to slow down.
• The reverse reaction is nonexistent at the start, but then picks up speed as more product is created.
kf[N2O4]
kr[NO2]2
Time
Rate
Equilibrium achieved(rates are equal)
• At equilibrium, the forward and reverse reactions are proceeding at the same rate.
• Once equilibrium is achieved, the amount of each reactant and product remains constant.
Chemical Equilibrium
Kf[N2O4]
Kf[NO2]2
Time
Rate
Equilibrium achieved(rates are equal)
This is a dynamic equilibrium, meaning that the reactions do not stop, but there is no net change in any concentrations.
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Once equilibrium is achieved, two important conditions apply:
(1) the forward and reverse reactions are proceeding at the same rate.
Chemical Equilibrium
(2) the amount of each reactant and product remains constant.
Kf[N2O4]
Kf[NO2]2
Time
Rate
Equilibrium achieved(rates are equal)
(This does not imply that the amount of reactants = amount of products.)
Chemical Equilibrium
It is important to note that equilibrium can be achieved regardless of whether you start with reactants or products, as long as there is sufficient material to get both processes going.
N2 (g) + 3H2 (g) 2NH3 (g)
Chemical Equilibrium
N2 (g) + 3H2 (g) 2NH3 (g)
In this graph, observe that the only substances initially present are nitrogen and hydrogen; there is no ammonia at the start.
In this graph, observe that the only substance initially present is ammonia; there is no nitrogen and hydrogen at the start.
Chemical Equilibrium
Regardless of the starting material, however, the same equilibrium concentrations of all three substances will eventually be reached.
N2 (g) + 3H2 (g) 2NH3 (g)
1 At equilibrium, _______________________.
A all chemical reactions have ceased
B the rates of forward and reverse reactions are equal
Cthe rate constants of the forward and reverse reactions are equal
D the value of the equilibrium constant is 1
E the limiting reagent has been consumed
2 Which of the following statements is NOT true about a reversible reaction at equilibrium?
A reactant and product concentrations are constant
B reactants and products remain in dynamic equilibrium
C reactant concentrations are equal to product concentrations
Dthe forward reaction occurs at the same rate as the reverse reaction
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3 To achieve equilibrium, you must have only reactants to start with.
True
False
4 Consider the equilibrium A + 3B <> 2C. Equilibrium can be reached if you start with:
A only A
B only B
C only C
5 Consider the equilibrium A + 3B <> 2C. Equilibrium cannot be reached if you start with:
A A & B
B only B
C only C
6 Consider the equilibrium 2 SO2 (g) + O2 (g) 2 SO3 (g). Equilibrium cannot be established when _________is/are in the container.
A 0.5 mol SO2 and 0.5 mol O2B 0.5 mol SO3
C 0.5 mol O2 and 0.5 mol SO3D 0.5 mol SO2
E 0.5 mol SO2 and 0.5 mol SO3
The Equilibrium Constant
• Recall that the definition of chemical equilibrium is when the rate of the forward reaction equals the rate of the reverse reaction.
N2O4(g) <>2NO2(g)
• Therefore, at equilibrium, we can set the two rate laws equal:
Rate of forward reaction = Rate of reverse reaction
kf [N2O4] = kr [NO2]2
• Rewriting this, it becomes
kf [NO2]2
kr [N2O4] =
The ratio of the rate constants is known as the equilibrium constant, K. The ratio simplifies to a ratio of products to reactants.
The Equilibrium Constant
kf [NO2]2
kr [N2O4] =Keq =
The value of Keq is constant for a specific reversible reaction at a certain temperature. Like rate constants, an equilibrium constant, Keq will only change when there is a change in temperature.
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The Equilibrium Constant
The equilibrium constant expression can be written from a balanced chemical equation
aA + bB cC + dD
according to the general format:
Kc = K = [C]c [D]d
[A]a [B]b
The Equilibrium Constant
Pure solids and liquids are not included in the calculation of the equilibrium constant. You can take their concentration to be 1, and not include them.
That's because their concentrations don't change during a reaction.
Molarity = density / molar mass = (g/L) / (g/mol) = mol/L
Since neither density nor molar mass varies for a pure liquid or pure solid, we take their molarities to remain constant.
The equilibrium constant for the reaction is
CH4 (g) + 2O2(g) CO2 (g) + 2H2O(l)
The Equilibrium Constant
K = [CO2]
[CH4] [O2]
2
The Equilibrium Constant
The equilibrium constant for the reaction is
2Cl2 (g) + 2H2O(g) 4HCl(g) + O2(g)
K = [HCl]4 [O2]
[Cl2]2 [H2O]
2
The Equilibrium Constant
The equilibrium constant for the reaction is
(CH3)4Sn(s) (CH3)4Sn(g)
K = [(CH3)4Sn]
7 The equilibriumconstant expression depends on the __________ of the reaction.
A stoichiometry
B mechanism C stoichiometry and mechanism D the quantities of reactants and products initially present
E temperature
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8 Which one of the following will change the value of an equilibrium constant?
A changing temperature
B adding other substances that do not react with any of the species involved in the equilibrium
C varying the initial concentrations of reactants
D varying the initial concentrations of products
E changing the volume of the reaction vessel
• If K >1, the reaction is productfavored; product predominates at equilibrium.
• If K<1, the reaction is reactantfavored; reactant
predominates at equilibrium.
What Does the Value of K Mean?
Reactants
Reactants
Products
Products
K > 1
K < 1
The direction from which equilibrium is achieved (starting with all products or all reactants) doesn't
matter.
It is only a convention that we calculate K by dividing the concentrations of products over
reactants, since the reaction proceeds both ways.
Unless specified, read the equation left to rightLeft side reactants; right side products.
But that convention makes it easy to understand the meaning of Keq.
Equilibrium 9 For a reaction at equilibrium, a value of K= 1 x 108 means that
A reactants are favoredB products are favoredC the reaction is spontaneousD the reaction is endothermic
10 For a reaction at equilibrium, a value of K = 4 x 1012 means that
A reactants and products are present in equal amounts
B the forward reaction is occurring faster than the reverse reaction
C the reverse reaction is occurring faster than the forward reaction
D reactants are favored
E products are favored
11 X <> Y + Z
What is the equilibrium constant expression for the reaction above?
A K = [X] / [Y] +[Z]
B K = [X] / [Y] [Z]
C K = [X] / [Y] [Z]
D K = [Y] + [Z] / [X]
E K = [Y] [Z] / [X]
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12 X <> Y + Z
Calculate the value of the equilibrium constant, K, for the reaction above if the equilibrium concentrations are:
[X] = 0.3 M, [Y] = 0.5 M, [Z] = 1.2 M
13 A + 2B <> CCalculate the value of the equilibrium constant, K, for the reaction above if the equilibrium concentrations are: [A] = 0.1 M, [B] = 0.2 M, [C] = 0.4 M
14 2A + B <> CThe value of the equilibrium constant, K, for the reaction above at 400 K is 100. Calculate the equilibrium concentration of C, given these equilibrium concentrations at 400 K: [A] = 0.1 M, [B] = 0.4 M
[C] = ____ M
15 X <> 2Y + Z The value of the equilibrium constant, K, for the reaction above at 350 K is 0.5. Calculate the equilibrium concentration of X, given these equilibrium concentrations at 400 K: [Y] = 2 M, [Z] = 1 M
[X] = ____ M
The Equilibrium Constant
Since pressure is proportional to concentration for gases in a closed system, the equilibrium expression can also be written in terms of pressure
where Pc = partial pressure of gaseous substance C PA = partial pressure of gaseous substance A and so forth for B and D
Recall that PA = XA(Ptot) where XA is the mole fraction of the gas and Ptot is total pressure.
Consider the generalized reaction
cC + dDaA + bB
Kp =(PA)
a(PB)b
(PC)c (PD)
d
16 What is the equilibrium expression for Kp for the reaction given.
2 O3 (g) 3 O2 (g)
A 3 PO2 / 2 PO3
B 2PO3 / 3 PO2C 3 PO3 / 2 PO2D (PO3)2 / (PO2)3
E (PO2)3 / (PO3)2
Kp =(PA)
a(PB)b
(PC)c (PD)
d
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From the Ideal Gas Law we know that
Rearranging it, we get
PV = nRT
P = RTnV
= [M] (the concentration)nV
So, P = [M] RT
Relationship Between Kc and Kp
Kp = ([C]cRT) ([D]dRT) ([A]aRT) ([B]bRT)
[C]c [D]d RTc+d [A]a[B]b RTa+b
= Kc x (RT) [(c+d) (a+b)]
Kp = Kc (RT) Δn
=
Relationship Between Kc and Kp
Since P = (n/V)RT = [M] RT, we can substitute as follows:
Kp =(PA)
a(PB)b
(PC)c (PD)
d
Therefore, the relationship between Kc and Kp becomes
Kp = Kc (RT)Δn
Δn = (moles of gaseous product) (moles of gaseous reactant)
Δn is the change in the number of moles of gas, which may be either positive or negative
R is the gas constant (0.0821 Latm/molK)
T is the absoluted temperature in Kelvin
Relationship Between Kc and Kp
where
17 Given the following reaction at equilibrium at 450oC, if PCO2 = 0.0160 atm, then what is the value of the equilibrium constant, Kp?
CaCO3 (s) CaO (s) + CO2 (g)
A 2.70 x 104
B 0.0160C 0.0821
D 7.23E 723
Kp =(PA)
a(PB)b
(PC)c (PD)
d
18 Given the following reaction at equilibrium, if Kc = 6.44 x 105 at 230oC, what is Kp?
2 NO (g) + O2 (g) 2 NO2 (g)
A 3.67 x 10 2
B 6.44 x 10 5
C 1.56 x 10 4
D 2.66 x 106
E 2.67 x 107
Kp = Kc (RT)Δn
19 Given the following reaction at equilibrium, if Kp = 1.05 at 250
oC, then Kc = ___?
PCl5 (g) PCl3 (g) + Cl2 (g)
A 3.90 x 106
B 2.45 x 102
C 1.05D 42.9
E 45.0 Kp = Kc (RT)Δn
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Manipulating Equilibrium Constants
We now consider how the value of Keq changes when:
• a reversible reaction is written in the reverse direction• the coefficients of a balanced equation are increased or decreased• two small reactions are added to yield an overall reaction
Manipulating Equilibrium Constants
Consider the reaction A <> 2B
Write the K expression for this reaction:
Now, consider the reaction 2B <> A
Write the K expression for this reaction:
Manipulating Equilibrium Constants
When a reaction is reversed, the new K expression is simply the reciprocal of the original.
[B]2 [A]original K =
[A] [B]2new K =
A <> 2B
2B <> A
20 At 250K, the equilibrium constant for the reaction X + 3Y Z is 8. What is the value of the equilibrium constant for the reaction Z X + 3Y?
A 0.125B 0.25
C 8
D 80
21 At 1000K, the equilibrium constant for the reaction 2A + B 2C is 0.02. What is the value of the equilibrium constant for the reaction 2C 2A + B?
A 0.02B 50C 100D 200
Manipulating Equilibrium ConstantsNow, consider the effect of multiplying all the coefficients in a balanced equation by a small whole number.
A 2B [B]2 [A]1Kc = = 0.2
(0.2)3 K'c = =3A 6B ([B]2)3 ([A]1)3
The equilibrium constant, K'c, of a reaction that has been multiplied by a small, whole number is the original equilibrium constant, Kc, raised to the power of that small, whole number.
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Manipulating Equilibrium ConstantsHere is another example:
N2O4(g) 2NO2
[NO2]2 [N2O4]1Kc = = 0.212
2N2O4(g) 4NO2
([NO2]2)2 ([N2O4]1)2
K'c = 0.0449
(0.212)2 K'c = =
The equilibrium constant, K'c, of a reaction that has been multiplied by a small, whole number is the original equilibrium constant, Kc, raised to the power of that small, whole number.
22 The value of Keq for the reaction A + B C + D is 0.25. The value of Keq at the same temperature for the reaction 2A + 2B 2C + 2D is __________.
A 0.25
B 2 x (0.25)
C 1/2 x (0.25)
D 1/ (0.25)
E (0.25)2
23 The value of Keq for the equilibrium H2(g) + I2(g) 2HI(g) is 900 at 25°C. What is the value of Keq for the equilibrium below?
½H2(g) + ½I2(g) HI(g)
A 900
B 900/2
C 900*2
D √900
E 9002
24 2 Cl2 (g) + 2 H2O (g) 4 HCl (g) + O2 (g)The Keq for the equilibrium above is 7.52 x 102 at 480oC. What is the value of Keq at this temperature for the reaction Cl2 (g) + H2O (g) 2 HCl (g) + 1/2 O2 (g)?
A 5.66 x 103
B 0.0376C 0.0752D 0.150E 0.274
25 At 550oC, Keq = 100 for the equilibrium 6A +2B 4C + 2D. What is the value of Keq at this temperature for the reaction 2C + D 3A + B?
A 0.1
B 0.02
C 50
D 200
E √200
Manipulating Equilibrium Constants
Consider a reaction that can be written as the sum of two or more steps. For example, the overall reaction A + B D + Ecan be written as the sum of these two steps:
Equation (1) A + B C
Equation (2) C D + E
Sum of Equations (1+2) A + B D + E
Write the K expression for these three equations.
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Manipulating Equilibrium Constants
Equation (1) A + B C
Equation (2) C D + E
Sum of Equations (1+2) A + B D + E
The equilibrium constant for a net reaction made up of two or more steps is the product of the equilibrium constants for the individual steps.
Write and compare the equilibrium expressions for these 3 reactions.
K3 = K3 x K2 =[C]
[A][B][D][E] [C]X
K3 = [D][E] [A][B]
[C] [A][B]K1 =
[D][E] [C]K2 =
The equilibrium constant for a net reaction made up of two or more steps is the product of the equilibrium constants for the individual steps.
Manipulating Equilibrium Constants
26 X > Y K1 = 0.3Y > Z K2 = 0.1
The equilibrium constant for the reaction X <> Z is _____
A 0.03
B 0.1
C 0.2
D 0.3
E 0.4
27 A > C + D K1 = 5A + B + C > 2D K2 = 6
The equilibrium constant for the reaction 2A + B <> 3D is _____
A 5
B 6
C 11
D 30
E Not enough information is given.
Solving Equilibrium ProblemsSo far, all of the equilibrium problems have been for a reaction at equilibrium.
The following problem gives initial concentrations (instead of equilibrium concentrations) and asks for calculation of K. We use an "ICE" chart, like the one shown below, for problems such as these.
Example: A + 2B <> C
A 2B C
(I) Initial concentration
(C) Change
(E) Equilibrium concentration
A closed system initially containing 1.000 x 103 M H2 and 2.000 x 103 M I2 at 448 °C is allowed to reach equilibrium. Analysis of the equilibrium mixture shows that the concentration of HI is 1.87 x 103 M. Calculate Kc at 448 °C for the reaction taking place, which is, H2 (g) + I2 (s) 2 HI (g)
Solving Equilibrium Problems
H2 (g) I2 (s) 2HI (g)
(I) Initial concentration
1.000 x 103 M 2.000 x 103 M
(C) Change
(E) Equilibrium concentration
1.87 x 103 M
• First, put in all of the information that is given. • Pay close attention to whether the given values are INITIAL concentrations or EQUILIBRIUM concentrations.
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H2 (g) I2 (s) 2HI (g)
(I) Initial concentration
1.000 x 103 M 2.000 x 103 M 0
(C) Change
(E) Equilibrium concentration
1.87 x 103 M
Note that the problem does not indicate that any product, HI, is initially present. Therefore, the starting concentration for HI is put down as 0.
Solving Equilibrium Problems
H2 (g) I2 (s) 2HI (g)
(I) Initial concentration
1.000 x 103 M 2.000 x 103 M 0
(C) Change + 1.87 x 103 M
(E) Equilibrium concentration
1.87 x 103 M
Now, we consider how to complete the chart. If [HI] starts at 0 and ends at 1.87 x 103 M , then the change must be + 1.87 x 103 M.
Solving Equilibrium Problems
H2 (g) I2 (s) 2HI (g)
(I) Initial concentration
1.000 x 103 M 2.000 x 103 M 0
(C) Change 1/2(1.87 x 103) M = 9.35 x 104 M
1/2(1.87 x 103) M = 9.35 x 104 M
+ 1.87 x 103 M
(E) Equilibrium concentration
1.87 x 103 M
Now, look at the stoichiometry of the reaction. Using the ratio of the coefficients, complete the "CHANGE" row.
Note that reactant concentrations will decrease as these substances get consumed.
Solving Equilibrium Problems
H2 (g) I2 (s) 2HI (g)
(I) Initial concentration
1.000 x 103 M 2.000 x 103 M 0
(C) Change 1/2(1.87 x 103) M = 9.35 x 104 M
1/2(1.87 x 103) M = 9.35 x 104 M
+ 1.87 x 103 M
(E) Equilibrium concentration
6.50 x 105 M 1.07 x 103 M 1.87 x 103 M
Since reactants get consumed, subtract the CHANGE amount from the INITIAL amounts to obtain theEQUILIBRIUM amounts.
Solving Equilibrium Problems
Now, we are ready to substitute the equilibrium concentrations into the equilibrium constant expression for the reaction.
Kc =[HI]2
[H2] [I2]
(1.87x103)2
(6.50 x 105) (1.07 x 103)=
= 51
Solving Equilibrium Problems
Note that an ICE chart may be completed using either moles or molarity.
If you use moles, make sure to divide by the volume to obtain molarity before substituting into the K expression.
Solving Equilibrium Problems
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28 Consider the reaction X <> YThe initial concentration of X is 4 M and the equilibrium concentration of Y is 1 M.What is the equilibrium amount of X?
A 3B 4
C 5
X Y
Initial 4
Change
Equilibrium 1
29 Consider the reaction A <> 2 B The initial concentration of A is 10 M and the equilibrium concentration of B is 2 M.What is the equilibrium amount of A?
A 7
B 8
C 9
D 11
E 12
A 2 B
Initial 10
Change
Equilibrium 2
30 Consider the reaction A + B <> 2 C The initial concentrations of A and B are both 5 mol and the equilibrium concentration of C is 4 mol.What is the TOTAL number of moles at equilibrium?
A 4B 6C 10D 14
A B 2 C
Initial 5 5
Change
Equilibrium 4
31 Consider the reaction 2A <> B The initial concentration of A is 8 M and the equilibrium concentration of B is 3 M.What is the equilibrium amount of A?
A 2B 5C 6
D 11
E 14
2 A B
Initial 8
Change
Equilibrium 3
Solving Equilibrium Problems
• If initial concentrations are given, then you should use an ICE chart.
• Many equilibrium problems ask you to calculate the value of the equilibrium constant.
• Other equilibrium problems give you the value of Kc or Kp and ask you to solve for an equilibrium concentration. This is illustrated in the next sample problem.
PCl5 PCl3 Cl2(I) Initial pressure
1.66 atm 0 0
(C) Change
(E) Equilibrium pressure
For the equilibrium PCl5 (g) <> PCl3 (g) + Cl2 (g)
Kp = 0.497 at 500 K. A gas cylinder is charged (filled) with PCl5 to an initial pressure of 1.66 atm. What are the partial pressures of all substances at equilibrium?
Solving Equilibrium Problems
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Since there are no equilibrium concentrations given, we use variables for the CHANGE row.
Solving Equilibrium Problems
PCl5 PCl3 Cl2(I) Initial pressure
1.66 atm 0 0
(C) Change x + x + x
(E) Equilibrium pressure
Now, we calculate equilibrium concentrations.
Solving Equilibrium Problems
PCl5 PCl3 Cl2(I) Initial pressure
1.66 atm 0 0
(C) Change x + x + x
(E) Equilibrium pressure
1.66 x x x
Write out the equilibrium constant expression, Kc.
Solving Equilibrium Problems
(x)2
(1.66 x)= = 0.497Kp =
(PCl2)(PCl3)(PPCl5)
PCl5 PCl3 Cl2(I) Initial pressure 1.66 atm 0 0
(C) Change x + x + x
(E) Equilibrium pressure
1.66 x x x
Solving Equilibrium Problems
(x)2
(1.66 x)= = 0.497Kp =
(PCl2)(PCl3)(PPCl5)
which simplifies to
x2 + 0.497x 0.825 = 0
A = 1B = 0.497C = 0.825
Use the quadratic equation to solve for x. Examine the two values that you obtain; one value will be negative and therefore incorrect.
PCl5 PCl3 Cl2(I) Initial pressure 1.66 atm 0 0
(C) Change x + x + x
(E) Equilibrium pressure
0.967 0.693 0.693
Solving Equilibrium Problems
Once you obtain the correct values, substitute them into the K expression to check your work.
(0.693)2
(0.967)= = 0.497Kp =(PCl2)(PCl3)(PPCl5)
The Reaction Quotient (Q)
When a system is not at equilibrium, it is useful to try to predict which reaction
(the forward or the reverse reaction) must be favored in order to reach equilibrium.
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The Reaction Quotient, Q, gives the same ratio the equilibrium expression gives, but for a system that is not at equilibrium.
The Reaction Quotient (Q)
• To calculate Q, one substitutes the initial concentrations of reactants and products into the equilibrium expression.
• Then, by comparing the values for Q and K, one can predict in which direction (forward or reverse) the reaction must proceed in order to achieve an equilibrium state.
The Reaction Quotient (Q)
If Q = K,
then we conclude that the system is already at equilibrium.
If Q > K,
then there is too much product; the reaction must proceed to the left in order to reach a state of equilibrium.
The phrase "proceed to the left" basically means that the reverse reaction must speed up while
the forward reaction slows down, in order for Q=K eventually.
If Q < K,then there is too much reactant; the
reaction must proceed to the right in order to reach a state of equilibrium.
The phrase "proceed to the right" basically means that the forward reaction must speed up while the reverse reaction slows down, in
order for Q=K eventually.
32 If K = 50 for a reaction at a temperature of 500 K, and Q = 12, then
A the reaction will proceed to the right to reach equilibrium
B the reaction will proceed to the left to reach equilibrium
C the reaction is already at equilibrium
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33 If K = 0.45 for a reaction at a temperature of 100 K, and Q = 6, then
A the reaction is already at equilibrium
B the reaction will proceed to the left to reach equilibrium
Cthe reaction will proceed to the right to reach equilibrium
Le Chatelier's Principle
Le Châtelier’s Principle
“If a system at equilibrium is disturbed by a change in temperature, pressure, or the concentration of one of the components, the system will shift its equilibrium position so as to counteract the effect of the disturbance.”
There are 3 possible stresses that can cause a system at equilibrium to no longer be at equilibrium:
• change in concentration (of a reactant or product),• change in pressure, and • change in temperature
We will examine the independent effect of each stress.
Le Châtelier’s PrincipleHow is equilibrium affected if we change the concentration?
+
Consider the following reaction:
The Haber ProcessSynthesis of ammonia from hydrogen and nitrogen
N2 (g) + 3H2 (g) 2NH3 (g)
Le Châtelier’s Principle
"take it and go" policy• If H2 is added to the system, the added hydrogen needs to be consumed.• How?• By reacting with nitrogen.• More N2 will be consumed with the added H2• More NH3 will be produced• If we increase the concentration of H2, equilibrium will shift to the right.
Initial equilibrium
H2
NH3
N2
H2 added at this timeEquilibriumreestablished
Time
Partial pressure
+
• What happens when you remove NH3?
• The system has to replace it to bring back the equilibrium
• More NH3 will be produced.
• As a result, [H2] and [N2] will get lower.
• We say that equilibrium will shift to the right as a result of this stress.
• We need large amount of NH3 for making fertilizers.
Le Châtelier’s Principle
Consider a decrease in the concentration of ammonia. How will equilibrium be affected?
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34 What happens to a reaction at equilibrium when a reactant concentration is lowered?
A Equilibrium shifts right; the reaction makes more products.
B Equilibrium shifts left; the reaction makes more reactants.
C The reaction makes more of both products and reactants, so equilibrium is unaffected.
35 What happens to a reaction at equilibrium when a product is removed from the reaction system?
A The reaction makes more products.
B The reaction makes more reactants.
CThe reaction makes more of both products and reactants, so equilibrium is unaffected.
36 What is the effect of adding more carbon dioxide to the following equilibrium reaction?CO2 (g) + H2O (l) H2CO3 (aq)
A More H2CO3 (carbonic acid) is produced.
B Equilibrium shifts right, toward the products.
C Equilibrium shifts left, toward the reactants.
D Both A and B.
Le Châtelier’s Principle
How will equilirbium be affected if we change volume/pressure?
Recall the Ideal Gas Law PV = nRT
What is the relationship between P and n?
There is a direct relationship between pressure and number of moles (or molecules).
Le Châtelier’s PrincipleHow will equilibrium be affected if we increase pressure?
N2 + 3H2 2NH3
• If the volume is decreased, it will increase the total pressure of the system.
• So the system will try to reduce the pressure by producing fewer moles of gas. • The reaction will favor producing fewer moles of gas.
• The reactant side has 4 moles of gas and the product side only 2 moles. Therefore, equilibrium shifts to the right, in this case, to reduce pressure.
Stress: Increasing pressure +/or reducing volumeEffect: Equilibrium shifts to the right there are fewer moles of gas
Le Châtelier’s PrincipleHow will equilibrium be affected if we decrease pressure?
N2 + 3H2 2NH3
• If the volume is increased, it will reduce the pressure of the system
• So the system will try to increase the pressure by producing more molecules or moles of gas.
• In this case, equilibrium will shift to the left, where there is a greater number of mole of gas.
Stress: Decreasing pressure/ increasing volumeEffect: Equilibrium shifts to the left there are more moles of gas
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37 How does an increase in pressure affect the following reaction at equilibrium?C2H2 (g) + H2 (g) C2H4 (g)
A Equilibrium shifts to the right; the reaction makes more products.
B Equilibrium shifts to the left; the reaction makes more reactants.
C The reaction makes more of both products and reactants, so equilibrium is unaffected.
38 Which of the changes listed below would shift the equilibrium of this reaction to the right?4HCl (g) + O2 (g) 2Cl2 (g) + 2H2O (g)
A Addition of Cl2 gas.
B Removal of O2 gas.
C Increase in pressure.
Le Châtelier’s Principle
If the temperature of the system is increased:
• The system should accept the thermal energy supplied to favor the endothermic reaction, and favor the forward reaction.• Equilibrium will shift to the right. • [PCl3] and [Cl2] increase while [PCl5] decreases.• Therefore, the value of K will increase.
How will equilibrium be affected if we change the temperature?
Consider this endothermic decomposition reaction.
PCl5 PCl3 + Cl2 ΔH = 88 KJ
Le Châtelier’s Principle
If the temperature of the system is lowered:
• The system should respond to the lowering of thermal energy by releasing heat to surroundings in an exothermic reaction. Therefore, the reverse reaction is favored because it is exothermic.• Equilibrium will shift to the left. • [PCl5] increases while [PCl3] and [Cl2] decrease.• Therefore, the value of K will decrease.
PCl5 PCl3 + Cl2 ΔH = 88 KJ
If we change the temperature:
At low temp, the purple hexa aqua species if favored. At high temp, the blue tetra chloro species is favored.
Le Châtelier’s Principle
at 1000Cat 250C
Many ions containing transition metals produce colored solutions. In the reaction above, the cation, Co(H2O)62+, yields a purple solution, while the anion CoCl42 produces a blue solution.
purple blueCo(H2O)6
2+(aq) + 4Cl(aq) CoCl42(aq) + 6H2O(l)
Do you think the reaction above is endothermic or exothermic?
purple blueCo(H2O)62+(aq) + 4Cl(aq) CoCl42(aq) + 6H2O(l) + heatexothermic
reaction
purple blueheat + Co(H2O)62+(aq) + 4Cl(aq) CoCl42(aq) + 6H2O(l)
Which reaction below do you think correctly represents the observation of these colors?
at 1000Cat 250C
Le Châtelier’s Principle
endothermic reaction
or
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39 For the reaction below, what is the effect of raising the temperature?
4A (g) + B (g) 3C ΔH = 405 kJ
A Equilibrium shifts to the right; the reaction makes more products.
B Equilibrium shifts to the left; the reaction makes more reactants.
C The reaction makes more of both products and reactants, so equilibrium is unaffected.
40 For the reaction below at equilibrium when the temperature is raised, the value of K will:
4A (g) + B (g) 3C ΔH = 405 kJ
A increaseB decreaseC remain constantD Not enough information.
41 For the reaction below, what is the effect of raising the temperature? X 2Y + Z ΔH = + 255 kJ
A Equilibrium shifts to the right and K will increase.
B Equilibrium shifts to the left and K will decrease.
C Equilibrium is unaffected and K stays constant. Significance of K value Equilibrium lies to the right (productfavored) or lies to the left (reactant favored).
Comparing Q and K The reaction must proceed to the right or proceed to the left in order to achieve equilbrium.
Le Chatelier's Principle Equilibrium shifts to the left or shifts to the right, in order to reestablish equilibrium.
Comparison of Equilibrium Terminology
Different terminology is required, depending on whether a system is:
a) at equilibriumb) trying to reach equilibriumc) was at equilibrium but had its equilibrium disturbed