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Now that we have learned the basic rules of dealing with equilibrium mathematics, lets take a look at the typical types of problems that you will encounter throughout the unit.
At Equilibrium
In many problems, the information will tell you that the system is already at equilibrium. If this is the case,
nothing further needs to be done other than plugging-and-chugging into your Kc or Kp equation.
Example 1:
At equilibrium, the following system is found to have [N2] = 2.4x10-5, [O2] = 3.1x10-3, and [NO]= 5.2x103.
Calculate Kc for the equation:
N2 (g) + O2 (g) <> 2 NO (g)
Based upon the above equation:
Kc =
[NO]2
[N2][O2]
Since the system is already at equilibrium, plug in the appropriate numbers in their spots in the equation:
Kc =
[NO]2
Kc =
[N2][O2]
[5.2x103]2
= 3.6x1014
[2.4x10-5][3.1x10-3]
Example 2:
At equilibrium, the following system is found to have PCl2 = 3.4x10-3, PH2O = 5.1x10-2, and PO2 = 7.2x10-4. If
Kp = 0.45, calculate the PHCl.
2 Cl2 (g) + 2 H2O (g) <> 4 HCl (g) + O2 (g)
Kp =
P4HCl PO2
P2Cl2 P2H2O
0.45 =
P4HCl (7.x10-4)
PHCl= 6.61x10-2
(3.4x10-3)2(5.1x10-2)2
AP Pirate Chemistry All text copyright Christopher Smith 2012. All pictures obtained from the web and assumed to be publicly
accessible. If you are the owner of a picture and want it removed, please email csmith@d211.org.
Dissociation
Instead of telling you what the equilibrium conditions are, you may instead be given starting information and
be told by what percent the system dissociates. Dissociation is simply how much of the starting material reacts
over to the other side. It is usually best to use what is called an ICE table.
ICE stands for
Initial Change Equilibrium
Or to put it another way, how much you start with (initial), how much it changes by (change) and what is left
over once equilibrium is reached (equilibrium). Lets see how this works.
Example 1:
For the equilibrium system:
PCl5 (g) <> PCl3 (g) + Cl2 (g)
If you start with 2 atm of PCl5 and the system dissociates 20% to reach equilibrium, calculate Kp.
Set up an ICE table
PCl5
Initial
2
Change
Equilibrium
<>
PCl3 +
0
Cl2
0
Now lets make the system undergo the required dissociation. Since we are starting with 2 atm and the problem says we dissociate by 20%, the system must lose:
20% (2 atm) = 0.4 atm
Initial
Change
Equilibrium
PCl5
2
-0.4
<>
PCl3 +
0
Cl2
0
But keep in mind that stoichiometry is still in effect here. If we lose 0.4 from the left side we must gain an appropriate amount on the right side:
PCl5 <>
PCl3 +
Cl2
Stoichiometric principles are now satisfied
Initial
2
0
0
Change
-0.4
+0.4
+0.4
Equilibrium
So now calculate what is left at equilibrium:
PCl5 <>
PCl3 +
Initial
2
0
Change
-0.4
+0.4
Equilibrium 1.6
0.4
Now that we have a value for each equilibrium spot,
plug the numbers into your Kp equation and solve:
Cl2
0
+0.4
0.4
(0.4)(0.4)
= 0.1
1.6
AP Pirate Chemistry All text copyright Christopher Smith 2012. All pictures obtained from the web and assumed to be publicly
accessible. If you are the owner of a picture and want it removed, please email csmith@d211.org.
Example 2:
For the equilibrium system:
2 H2S (g) <> 2 H2 (g) + S2 (g)
If you start with 0.25 atm of H2S and the system dissociates 4% to reach equilibrium, calculate Kp.
Set up an ICE table
2 H2S <>
Initial
0.25
Change
Equilibrium
Calculate the dissociation:
2 H2 +
0
S2
0
4% (0.25) = 0.01
But note that the stoichiometry in the above equation is not a 1:1:1 ratio. Note that you only get 1 S2 mole for
every 2 H2S moles. You must take this into account just like we did in the stoichiometry section of the class:
Initial
Change
Equilibrium
2 H2S <>
0.25
-0.01
0.24
2 H2 +
0
+0.01
0.01
Kp = P2H2PS2
P2H2S
S2
0
+0.005
0.005
(0.01)2(0.005)
= 8.68x10-6
(0.24)2
Example 3:
For the equilibrium system: 2 NH3(g) <> N2 (g) + 3 H2 (g)
If you start with 0.015 M of NH3 and by the time equilibrium is established, there is 0.0009 M of H2 present,
calculate the % dissociation of the NH3.
Set up an ICE table
2 NH3 <>
Initial
0.015
Change
Equilibrium
Initial
Change
Equilibrium
2 NH3 <>
0.015
N2 +
0
3 H2
0
N2 +
0
3 H2
0
0.0009
Initial Conditions
AP Pirate Chemistry All text copyright Christopher Smith 2012. All pictures obtained from the web and assumed to be publicly
accessible. If you are the owner of a picture and want it removed, please email csmith@d211.org.
Since you started with 0 and ended with 0.009 M H2 it must have increased by 0.009 M
Initial
Change
Equilibrium
2 NH3 <>
0.015
N2 +
0
3 H2
0
+0.0009
0.0009
Now apply stoichiometric principles in the correct direction. You only get 1 N2 for every 3 H2 moles and you
only use 2 NH3 moles for every 3 moles of H2
Initial
Change
Equilibrium
2 NH3 <>
0.015
-0.0006
N2 +
0
+0.0003
3 H2
0
+0.0009
0.0009
2 NH3 <>
0.015
-0.0006
0.0144
N2 +
0
+0.0003
0.0003
3 H2
0
+0.0009
0.0009
Initial
Change
Equilibrium
The problem is asking you for the % dissociation. Remember that a % is simply the part over the total so a %
dissociation is the dissociation (change) over the total (initial):
% dissociation = Change
Initial
0.0006
*100% = 4%
0.015
Example 4:
A system starts with 3 atm of N2O4. At equilibrium, there is 0.50 atm of NO2 present. What is the % dissociation of N2O4?
Initial
Change
Equilibrium
N2O4 <>
3
-0.25
2.75
2 NO2
0
+0.5
0.5
% dissociation = Change
Initial
0.25
*100% = 8.3%
AP Pirate Chemistry All text copyright Christopher Smith 2012. All pictures obtained from the web and assumed to be publicly
accessible. If you are the owner of a picture and want it removed, please email csmith@d211.org.
Q vs. K
All of the problems we have seen so far have not been at equilibrium to begin with and it has been obvious
why not. If you examine every previous problem, at least one of the species present has had an initial value of
zero. A system cannot be at equilibrium if a species is at zero so the reaction must go towards that side to
make at least a little bit of that species. But what if you are given initial conditions where the species are all
non-zero values? Is the system at equilibrium? How we will know? If it is not at equilibrium, what direction
will the reaction proceed, towards the reactants or the products? Lets examine a typical problem of this sort:
Example 1: For the reaction seen below, the initial conditions are made so that
PCO = 2.5 atm PBr2 = 1.4 atm PCOBr2 = 5.2 atm
CO (g) + Br2 (g) <> COBr2 (g)
Kp = 14.5
Is the system at equilibrium? If not, which way will the reaction proceed; left or right?
First, how do we know if a system is at equilibrium? The ratio of products to reactants will equal K, right?
Lets do a test case called Q.
Q = reaction quotient
It is a test case for K
In all respects, Q is the same thing as K; it just might not be at equilibrium. Lets take a look:
CO (g) +
Br2 (g) <>
COBr2 (g)
Initial
2.5
1.4
5.2
Calculate Q (which is the same format as Kp) so
Q = PCOBr
PCOPBr2
5.2
= 1.49
(2.5)(1.4)
Is the system at equilibrium? If it was at equilibrium, the value would have to be 14.5 as stated above in the
problem. The system is clearly not at equilibrium because 1.49 does not equal 14.5 or:
QK
For the reaction to be at equilibrium, Q must equal K. So what, then, has to happen to the equation? Does Q
have to get bigger or smaller? Q must get bigger because 1.49 < 14.5
Since Q and K are both:
Products
the only way for Q to get bigger is to go to the products side
Reactants
By going to the products side, the numerator gets bigger, the denominator gets smaller and the ratio of products to reactants increases until Q = K. If Q was instead too BIG, then the reaction would proceed from the
products towards the reactants, thus making the numerator smaller and the denominator bigger so that Q got
smaller until again, Q = K. To summarize:
Example 2:
For the reaction:
H2 (g) + I2 (g) <> 2 HI (g)
Is the reaction at equilibrium if
[H2] = 0.42 [I2] = 0.67
If not at equilibrium which way will the reaction proceed?
First step is to calculate Q
Q=
[HI]2
[H2][I2]
Kc = 0.754
[HI] = 0.96
0.962
= 3.28
(0.42)(0.67)
Q = [H3O+1][N3-1]
[HN3]
(1x10-9)(2x10-4) = 1x10-7
2x10-6
Kc = 5x10-22
[H3PO4] = 0.01
Q=
[H3O+]3[PO4-3]
[H3PO4]
(3x10-3)3(5x10-24)
= 1.35x10-29
0.01
Thus the system is NOT at equilibrium and because Q is too small, the system will proceed to the right
side
AP Pirate Chemistry All text copyright Christopher Smith 2012. All pictures obtained from the web and assumed to be publicly
accessible. If you are the owner of a picture and want it removed, please email csmith@d211.org.
Initial
Change
Equilibrium
C3H7CH3 (g)
0
We can clearly see that this equation is not at equilibrium because the products are starting at a value of 0. So
we know the reaction will proceed to the right; what we dont know is how FAR the reaction will proceed to
the right. Because of this, we can set the change value of the problem as x because we dont know! So:
Initial
Change
Equilibrium
C3H7CH3 (g)
0
+x
x
We now have values for each of the equilibrium substances. We can also write the Kc equation for this and
insert its value from the given information above so:
KC =
[C3H7CH3]
[C4H10]
2-x
=3
Example 2:
The system below has a Kp = 20. Calculate the equilibrium pressures of all species if
PN2 = 0.25 and PO2 = 0.25
N2 (g) + O2 (g) <> 2 NO (g)
Initial
Change
Equilibrium
Kp =
N2
+
0.25
-x
0.25 x
P2NO
O2
<>
0.25
-x
0.25 x
20 =
PN2PO2
2 NO
0
+2x
2x
(2x)2
(0.25 x)2
(2x)
4.47 =
(0.25 x)
1.124.47 x = 2x
1.12 = 6.47x
x = 0.173
Initial
Change
Equilibrium
N2
+
0.25
-0.173
0.077
O2
<>
0.25
-0.173
0.077
2 NO
0
+2(0.173)
0.346
Double-check to make sure you have the right answers by plugging back into K:
Kp =
P2NO
PN2PO2
Kp =
(0.346)2
(0.077)2
= 20.2
AP Pirate Chemistry All text copyright Christopher Smith 2012. All pictures obtained from the web and assumed to be publicly
accessible. If you are the owner of a picture and want it removed, please email csmith@d211.org.
Example 3:
For the equation:
SO2Cl2 (g) <> SO2 (g) + Cl2 (g)
Kp = 3.4
If enough SO2Cl2 is put into a container so its pressure is 5 atm, what is the total pressure in the container?
Initial
Change
Equilibrium
SO2Cl2 <>
5
-x
5-x
PSO2PCl2
Kp =
PSO2Cl2
17-3.4x = x2
3.4 =
SO2
0
+x
x
Cl2
0
+x
x
x2
5-x
0 = x2 + 3.4x +17
x = 2.76
Initial
Change
Equilibrium
SO2Cl2 <>
5
-2.76
2.24
SO2 +
0
+2.76
2.76
Cl2
0
+2.76
2.76
But the problem asks for the total pressure in the system at equilibrium so:
Ptot = 2.24 + 2.76 + 2.76 = 7.76 atm
AP Pirate Chemistry All text copyright Christopher Smith 2012. All pictures obtained from the web and assumed to be publicly
accessible. If you are the owner of a picture and want it removed, please email csmith@d211.org.
Example 4:
For the equation:
NH4HS (s) <> NH3 (g) + H2S (g)
Kp = 4.8
If 100 grams of NH4HS are placed into a 15 L container at 500 K, how many grams of the solid remain at equilibrium?
Were going to have to use our knowledge of gas laws for this problem. First it is important to recognize that
the solid NH4HS will dissociate by some amount x so that the products are each made. What is strange is that
the x for the NH4HS will not actually be used in our calculations for K, though, because it is a solid. Lets set
up the ICE table:
Initial
Change
Equilibrium
H2S (g)
0
+x
x
Kp = PNH3PH2S =
x2 = 4.8
x = 2.19
Since x = 2.19 atm, we need to be able to turn this into grams of NH4HS.
Using our gas laws knowledge and the equation PV = nRT we can do this:
PV = nRT
AP Pirate Chemistry All text copyright Christopher Smith 2012. All pictures obtained from the web and assumed to be publicly
accessible. If you are the owner of a picture and want it removed, please email csmith@d211.org.