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CHEM 300 Friday Session 4, 9/25/15

Sizes of ions:

KEY

1)Silver (I) chloride has a pKsp of 9.74. If you stir 10.0 mol AgCl
into water to make 0.500 L solution, what will be the aqueous
concentrations of silver and chloride ions at equilibrium?
(Note: Ignore activities for this problem.)
AgCl(s) Ag+(aq) + Cl-(aq)
Ksp = 10-9.74 = 1.82 x 10-10 = [Ag+][Cl-] = x2
x = 1.348 x 10-5 M (aka 13.48 M) of each ion for a fully
saturated solution.

If all of the solid could dissolve, the concentration of each ion


would be
10.0 mol/0.500 L = 20.0 M (above saturation), so choose
the saturation concentration instead.

2)Silver (I) chloride has a pKsp of 9.74. If you stir 10.0 mol AgCl
and 10.0 mol KCl into water to make 0.500 L solution, what
will be the aqueous concentrations of silver and chloride ions
at equilibrium? (Note: Ignore activities for this problem.)
If using an ICE table to set up the problem, the treatment is
the same as if you were starting with the equilibrated
(saturated) solution from Q1 and adding KCl to disturb it.
Adding excess product (Cl-) will push the equilibrium
backward, forcing some AgCl to precipitate out of solution.
AgCl(s) Ag+(aq) + Cl-(aq)

AgCl
(s)

[Ag+]

[Cl-]

Initial

--

13.48 M

13.48 M + 20.0 M

Change

--

-x

-x

13.48 M x

33. 48 M - x

Equilibriu -m

Ksp = 1.82e-10 = (1.348e-5 x)(3.348e-5 x)


Do algebraic rearrangement to get equation in the quadratic
format:
x2 4.696e-5x + 2.69e-10 = 0
Solve this quadratic equation for two possible values of x:
x = 40.3 M OR 6.68 M (only the latter makes sense, use that)
So [Ag+] = 6.8 M and [Cl-] = 26.8 M

(Side note: Would ionic strength have been an issue in this


case? Summing effects of [K+], [Cl-] and [Ag+], = 27 M,
which is quite low.)

3)Silver (I) chloride has a pKsp of 9.74. If you stir 10.0 mol AgCl
and 25.0 mmol NaNO3 into water to make 0.500 L solution,
a) What will be the aqueous concentrations of silver and
chloride ions at equilibrium? (Notes: Use the appropriate
Debye-Hckel equation, and do not ignore activity
coefficients in this problem.)
Compared to Q2, a common ion effect is not an issue, but the
ionic strength from added NaNO3 will be.
= [(0.0250 mol Na+/0.500 L)(+1)2 + (0.0250 mol
NO3-/0.500 L)(-1)2 + (13.48 M Ag+)(+1)2 + (13.48 M Cl-)(-1)2] =
0.050013 M
For Ag and Cl activity coefficients, use a normal form of DH.
Both ions will be treated as either:
2

log i

0.51 zi
1 0.33 i

(an alternate version, where is ion size in

OR

(from book, where is ion size in pm)


Ag = 10^-[(0.51)(1)2(0.050013)1/2/[1 + (0.33)(2.50 )
(0.050013)1/2]] = 0.8011
Cl = 10^-[(0.51)(-1)2(0.050013)1/2/[1 + (0.33)(3.00 )
(0.050013)1/2]] = 0.8065
Ksp = 1.82 x 10-10 = [Ag+] Ag [Cl-]Cl = x2(0.8011)(0.8065)

x = 1.678 x 10-5 M (aka 16.78 M) for each ion


b)

Why did the addition of NaNO3 in this case effect a


change in solubility compared to Question 1?

The concentrations in Q3 are a little higher than those determined


in Q1. In Q1 at much lower ionic strength, each was closer to
unity (and so we ignored activity). Addition of more ions from
NaNO3 has increased . At this higher , calculated values are
<1 but Ksp is still the same. Therefore, ion solubility must be
higher (concentrations increase) compared to Q1.
4)Describe the difference between concentration and activity.
How are they related to each other?
Concentration is the theoretical amount of substance (such as an
ion) in solution under ideal conditions (i.e., no effect of ionic
strength on the substance). Activity is a value in which the
concentration is modified by an activity coefficient accounting for
the nonideal environment of the solution (including the effect of
ionic strength). The relationship is Ac = [C]c; A values are properly
used in equilibrium expressions.