Solubility & Solubility Product: Basic Chemistry For Physics & Biology

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Solubility & Solubility

Product
Basic Chemistry for Physics & Biology
Sri Kadarwati, Ph.D.
Solubility
“degree to which a substance dissolves in a solvent to make a solution (usually expressed
as grams of solute per litre of solvent).”

1. Insoluble – less than 1 gram dissolves in a liter


2. Slightly soluble 1-10 grams dissolves in a liter
3. Sparingly soluble 10-30 grams dissolves in a liter
4. Soluble – more than 30 grams dissolve in a liter
5. Precipitate – what comes out of solution when a compound that is formed is not soluble
6. Filtration– a great way to separate your precipitate from the solution!
7. Saturated solution – a solution that has the maximum amount of the compound dissolved into
solution
8. Supersaturated solution – one that has more than the maximum dissolved. This is done usually
by forming a saturated solution in hot water, and then letting the solution very slowly cool
without any seed crystals present
Solubility rules
01 Salts of the alkali metals, plus NH4+, are
usually soluble. This includes Li+, Na+, K+,
06 Hydroxides are insoluble, except for the
alkali metals which are soluble, and the
Rb+, Cs+ alkaline earth metals Mg2+, Ca2+, Sr2+, Ba2+
which are slightly soluble
02 Nitrates, with the NO3– ion, are always soluble.
So are acetates, chlorates and perchlorates.

03 Chlorides, bromides and iodides are soluble, 07 Sulfides are highly insoluble, except for the
alkali metals and alkaline earth metals
except for Ag+, Pb2+, & Hg22+
08 Carbonates, Chromates, phosphates, fluorides
04 Silver compounds are insoluble, except for
silver nitrate and silver acetate
are insoluble, except for the alkali metals and
NH₄⁺

05 Sulfates are soluble, except for Ca2+, Sr2+, Ba2+,


Pb2+, & Ag2+
Interesting Solubility Facts & Exceptions
01 Potassium chlorate, bromate and perchlorate are
only slightly soluble in cold waterused to
05 Bromates and formates are generally soluble

separate potassium from sodium in solution.


06 Copper (I) halides are insoluble
02 Sodium acetate is so soluble in water
difficult to form a super-saturated solution 07 Lead, mercury (II) and silver sulfate are
slightly soluble
Rubidium formate, thallium formate, and
03 silver perchlorate are 3 of the most highly 08 Sulfides are one of the most insoluble ions.
soluble compounds (over 5,000 g/L at room T)  often added to precipitate out lead. One of
the most insoluble ionic compounds is
04 A solution of equal parts thallium formate and
thallium malonate (Clerici solution) has
mercury (II) sulfide.

possibly the highest density minerals to be 09 Oxalates are highly insoluble, except for Na+,
K+ & NH4+. Even rubidium and cesium
separated by density.
oxalate are insoluble.
r t
C ha
i li ty
l u b
So
Solubility Quotient & Solubility
Product Constant
Spontaneous VS
Equilibrium state
Condition of Qs and Ksp

Q o Spontaneous dissolution
o Not saturated yet  [ions] in
solution < solubility
Illustration
When PbCl2 is dissolved in water, and the
concentration of Pb2+ and Cl- in the solution < its
solubility, so the product of their concentration
[Pb2+]*[Cl-]2 would be Qs
VS
s
Ks
PbCl2  Pb2++ 2Cl−
o Equilibrium state of system Qs = [Pb2+]*[Cl-]2
o Saturated solution  [ions] in
When saturated solution of PbCl2 is obtained:
solution = solubility
PbCl2 ⇌ Pb2++ 2Cl−
The concentration of Pb2+ and Cl- in the solution = its
p solubility.
The product of their concentration [Pb2+]*[Cl-]2
would be Ksp

2+ - 2
Does the precipitation occur?
Condition REQUIREMENT
No precipitation occurs
(unsaturated solution)
Qs < Ksp

Precipitation starts to occur


(saturated and over-saturated Qs ≥ Ksp
solution)
Example Problem-1

Problem Solution
If solid PbCl2 equilibrates with pure PbCl2 ⇌ Pb2++ 2Cl−
water, what are [Pb2+] and [Cl—] in s 2s
the solution at equilibrium? Ksp = [Pb2+] [Cl-]2
[Ksp (PbCl2) = 1.7 × 10—5]
Ksp = s (2s)2 = 4s3 = 1.7 × 10—5
s = 1.62 x 10-2 mol/L
[Pb2+] = s = 1.62 x 10-2 mol/L
[Cl-] = 2s
= 2* 1.62 x 10-2 mol/L
= 3.24 x 10-2 mol/L
Example problem-2
common ion effect

Calculate the solubility of PbCl2, in molL—1, in a solution of 0.15 M


MgCl2. (Ksp for PbCl2 is 1.7 x 10 —5)
Solution:
MgCl2  Mg2+ + 2Cl-
0.15 M 0.15 M 0.3 M
PbCl2 ⇆ Pb2+ + 2Cl-
s 2s + 0.3M (since 2s <<< 0.3M, so 2s+0.3M ~ 0.3M)
Ksp = [Pb2+] [Cl-]2 = s * (0.3)2 = 1.7 x 10-5  s = 1.9 x 10-4 mol/L (<<s in water only)
Example problem-3
Problem: Solution:
PbCl2 has Ksp = 1.7 × 10—5. If Pb(NO3)2 + 2KCl  PbCl2 + 2KNO3 (suppose 100 mL each)
equal volumes of 0.030 M 3 mmol 3mmol
Pb(NO3)2 and 0.030 M KCl 1.5mmol 3 mmol 1.5 3mmol
1.5 0 1.5 3mmol
are mixed, will precipitation Pb(NO3)2  Pb2+ + 2NO3- Qs = [Pb2+] [Cl-]2
occur?
1.5 mmol 1.5 3mmol = (1.5+1.5)mmol/200mL *
PbCl2 ⇆ Pb2+ + 2Cl- (3mmol/200mL)2
1.5 1.5 3 mmol = 3.375 x10-6 <<<Ksp 
will not precipitate
Example Problem-4
How much solid Pb(NO3)2 must be added to 1.0 L of 0.0010 M Na2SO4
solution for a precipitate of PbSO4, [Ksp = 1.6 × 10—8] to form?
Solution:
Pb(NO3)2 + Na2SO4  PbSO4 + 2NaNO3 (solid Pb(NO3)2 does not cause a volume change)

0.001 mol
Na2SO4 2Na+ + SO42-
0.001 0.002 0.001 mol
PbSO4 precipitate will form when Qs of PbSO4 = Ksp PbSO4= 1.6 x 10-8


[Pb2+] needed so that Qs = [Pb2+] [SO42-] = Ksp
[Pb2+] = Ksp/ [SO42-] = 1.6 x 10-8/0.001 mol/L = 1.6 x10-5 mol/L
[Pb2+] in solution would be THE SAME as [Pb(NO3)2] needed (same coefficient).
Pb(NO3)2  Pb2+ + 2NO3-
In 1 L solution, mol Pb(NO3)2=1.6x10-5 mol.
Colligative
Properties
Basic Chemistry for Physics & Biology
Sri Kadarwati, Ph.D.
Definition
“the physical changes resulted from adding solute to a solvent”

 depend on how many solute particles are present, but do NOT depend on the type of
solute.

Decrease in vapor pressure Freezing point depression


The vapor pressure of a solvent in a solution is The freezing points of solutions are all lower than
always lower than that of the pure solvent that of the pure solvent. The difference is directly
Raoult’s law. psolution = Xsolvent *p0solvent proportional to the molality of the solute.

∆Tf = Kf solvent * msolute (always positive)


The vapor pressure lowering is directly
proportional to the mole fraction of the solute.
Tf = Tf solvent – ∆Tf
∆p = p0solvent –psolution= p0solvent –Xsolvent *p0solvent solution

∆p = (1- Xsolvent) *p0solvent = Xsolute *P0solvent


Colligative Properties
Boiling point elevation
The boiling points of solutions are all
higher than that of the pure solvent. Osmotic Pressure
Difference between the boiling points of the
The osmotic pressure of a solution is the
pure solvent and the solution is proportional
pressure difference needed to stop the
to the molality of the solute particles.
flow of solvent across a semipermeable
∆Tb = Kb solvent * msolute (always positive) membrane.
The osmotic pressure of a solution is
Tb solution = Tb solvent + ∆Tb proportional to the molar concentration of the
solute particles in solution.
Π = Msolute R T
Example problem-1
Problem Solution
The vapor pressure of pure benzene (C6H6) is For ideal solution, Raoult’s law is applied
100.0 torr at 26.1 C. Calculate the vapor
o
psolution = Xsolvent * p0solvent
pressure of a solution containing 24.6 g of
camphor (C10H16O) dissolved in 100.0 mL of
psolution = Xben * p0ben
benzene. The density of benzene is 0.877 g/mL.
= (nben/(nben+ncam)) * 100 torr

nben = Wben/Mwben
= (⍴ben* Vben)/MWben
= (100 mL x 0.877 g/mL)/78.1 g/mol)
= 1.12 mol
ncam = Wcam/Mwcam
= 24.6 g/152.2 g/mol
= 0.162 mol
Example problem-2
Problem Solution
Tf solution = Tf water - ∆Tf
Ethylene glycol (EG), = Tf water – (Kf water * mEG)
CH2(OH)CH2(OH), is a common = 0 oC – (1.86 oC/m *
automobile antifreeze. Calculate the WEG/(MWEG * Wwater))
freezing point of a solution = 0 oC –(1.86 oC/m *
containing 651 g of EG in 2505 g of 651 g/(62.1 g/mol*2.505kg)
water. = 0 oC –(1.86 oC/m * 4.185 m)
= 0 oC –(7.784 oC) = ……………oC
Would you keep the substance in
your car radiator during the In summer, the weather is hotter.
summer? Calculate the Tb of solution to decide to keep the EG solution to
prevent the fast boiling of water.
The molar mass of EG is 62.01 g/mol. Tbsolution = Tbwater + ∆Tb
For water, Kf = 1.86 oC/m & Kb = 0.52
= Tbwater + (Kbwater*mEG)
o
C/m
= 100 oC + (0.52 oC/m * 4.185 m)
= 102.1762 oC  IMPORTANT to keep EG solution
Example Problem-3
Problem: Solution:
You are examining forensics data for a court case Tbsolution = TbEt + ∆Tb
and need to identify an anelgesic (pain killer). It 78.86 oC = 78.5 oC + ∆Tb  ∆Tb = 0.36 oC
could be either acetylsalicylic acid (aspirin), ∆Tb = Kb *msolutes
ibuprofen (advil) or acetaminophen (tylenol). A 0.36 K = 1.23 K/m * msolutes  msolutes= 0.36 K/1.23 K/m
mixture of the unknown is prepared by mixing 10.0 = 0.2927 m
g of unknown and diluting to 250 mL with ethanol. Wsolution = Vsolution * rhosolution = 250 mL * 0.8 g/mL = 200 g
The density of this solution is 0.80 g mL-1. Wsolvent = Wsolution – Wsolute = 200 g- 10 g = 190 g
Identify the unknown if: m = nsolute /Wsolvent = Wsolute/(Mwsolute*Wsolvent)
a. The boiling point of this mixture is 78.86 °C. 0.2927 mol/kg = 10 g/(MWsolute *0.19 kg)
KbET= 1.23 K/m MWsolute = 10 g/(0.2927 mol/kg * 0.19 kg) = 179.8 g/mol
b. The osmotic pressure of this mixture is 5.43 atm
at 25 °C. Π = M R T = (nsolute/Vsolution ) *R * T
5.43 atm = (nsolute /0.25 L) * 0.082 L atm/molK * 298 K
nsolute = (5.43 atm * 0.25 L) /(0.082 L atm /molK * 298 K)
= 0.056 mol
(W/MW)solute = 0.056 mol
MWsolute = Wsolute/n solute = 10 g/0.056 mol = 178.57 g/mol

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