STOIKIOMETRI LARUTAN

Solutions
• Solutions are homogeneous mixtures of two or
more pure substances.
• In a solution, the solute is dispersed uniformly
throughout the solvent.
 Solutions

How does a solid dissolve into

a liquid?

What ‘drives’ the dissolution

process?

What are the energetics of

dissolution?
 How Does a Solution Form?
1. Solvent molecules attracted to surface ions.
2. Each ion is surrounded by solvent molecules.
3. Enthalpy (DH) changes with each interaction broken or
formed.

Ionic solid dissolving in water

How Does a Solution Form
The ions are solvated
(surrounded by
solvent).
If the solvent is water,
the ions are hydrated.
The intermolecular force
here is ion-dipole.
 Degree of saturation

• Supersaturated
 Solvent holds more solute than is normally possible at
that temperature.
 These solutions are unstable; crystallization can often
be stimulated by adding a “seed crystal” or scratching
the side of the flask.
 Degree of saturation

Unsaturated, Saturated or Supersaturated?

 How much solute can be dissolved in a solution?

 Chap 13:
Ways of Expressing Concentrations of Solutions
 Mass Percentage

mass of A in solution
Mass % of A =  100
total mass of solution
 Parts per Million and
Parts per Billion

Parts per Million (ppm)

mass of A in solution
ppm =  106
total mass of solution

Parts per Billion (ppb)

mass of A in solution
ppb =  109
total mass of solution
 Mole Fraction (X)
moles of A
XA =
total moles in solution

• In some applications, one needs the mole

fraction of solvent, not solute—make sure
you find the quantity you need!
 Molarity (M)

mol of solute
M=
L of solution

• Because volume is temperature dependent,

molarity can change with temperature.
 Molality (m)

mol of solute
m=
kg of solvent

Because neither moles nor mass change

with temperature, molality (unlike molarity)
is not temperature dependent.
Ma
ss/
Ma
ss
s
ole
s /M
le
Mo

/L M
le s ole
Mo s /M
as
s
Concentration of Solution

Solvent Solute
 Concentration of Solution

Moles of solute Mol

(M) = =
•Molarity Liter of solution L
amount of solute (g or ml)

•Parts ratio = amount of solution (g or ml)

(102) or (106) or (109)

•Mole Fraction (c) = Moles of solute

Total moles of solution

Moles of solute
•Molality (m) = Kilograms of solvent
 Molarity

NaCl Molarity Example Problem 1

12.6 g of NaCl are dissolved in water making 344mL of solution.

Calculate the molar concentration.

 1molNaCl 
12.6 g NaCl  
moles solute  58.44 gNaCl 
M= =
L solution  1L 
344 mL   solution
 1000mL 
= 0.627 M NaCl
 Molarity

NaCl Molarity Example Problem 2

How many moles of NaCl are contained in 250.mL of solution with a

concentration of 1.25 M?

moles solute therefore the

M= solution contains
L solution
 1L  1.25 mol NaCl
250. mL   = 0.250 L solution
 1000mL  1 L solution
Volume x concentration = moles solute
 1.25 mol NaCl 
0.250 L solution   = 0.313 mol NaCl
 1 L solution 
 Molarity

NaCl Molarity Example Problem 3

What volume of solution will contain 15 g of NaCl if the solution
concentration is 0.75 M?

moles solute therefore the

M= solution contains
L solution
 1 mol NaCl  0.75 mol NaCl
15 g NaCl   = 0.257 mol
 58.44 g NaCl  1 L solution
moles solute ÷ concentration = volume solution
 1 L solution 
0.257 mol NaCl  = 0.34 L solution
 0.75 mol NaCl 
 % Concentration

mass solute
• % (w/w) = x 100
mass solution

• % (w/v) = mass solute

x 100
volume solution

• % (v/v) = volume solute

x 100
volume solution

Mass and volume units must match.

(g & mL) or (Kg & L)
 % Concentration
Example Problem 1 (Solid in a Liquid)

What is the concentration in %w/v of a solution containing 39.2 g of potassium nitrate in 177 mL
of solution?

mass solute 39.2 g

% (w/v) =  100  100 = 22.1 % w/v
volume solution 177 mL

Example Problem 2 (Liquid in a Liquid)

What is the concentration in %v/v of a solution containing 3.2 L of ethanol in 6.5 L of solution?

volume solute 3.2 L

% (v/v) =  100  100 = 49 % v/v
volume solution 6.5 L
 % Concentration
Example Problem 3
What volume of 1.85 %w/v solution is needed to
provide 5.7 g of solute?

% (w/v) =
1.85 g solute
100 mL solution
We know: We want to get:

g solute
g solute and mL solution
mL solution

 100 mL solution 
5.7 g solute   = 310 mL Solution
 1.85 g solute 
g solute ÷ concentration = volume solution
• [HCl] : 37% (b/b); massa jenis HCl : 1,19 g/mL. Berapa Molaritas HCl
tersebut?
Tentukan konsentrasi % (b/v) HCl pekat. Gunakan rumus berikut :

% (b/v) : % (b/b) x massa jenis

% (b/v) : 37% (g/g) x 1,19 g/mL
% (b/v) : 44,03% (b/v)
44,03% (b/v) artinya 44,03 gram dalam 100 mL larutannya.

Tentukan konsentrasi dalam Molaritas HCl pekat.

M : mol / L
M : (massa / Mr) / L
M : massa / (Mr x V)
M HCl : m. HCl / (Mr HCl x V)
M HCl : 44,03 g / (36,5 g/mol . 100 mL . 10^-3 L/mL)
: 12,0630 mol / L
: 12,0630 M
 Parts per million/billion (ppm & ppb)
mass solute mg
• ppm = × 106 or = ppm
volume solution L

• ppb = mass solute g

× 109 or = ppb
volume solution L
AND
Mass and volume units must match. For very low
concentrations:
(g & mL) or (Kg & L)
ng = ppt
parts per trillion
L
 ppm & ppb
Example Problem 1
An Olympic sized swimming pool contains 2,500,000 L of
water. If 1 tsp of salt (NaCl) is dissolved in the pool, what is
the concentration in ppm?

1 teaspoon = 6.75 g NaCl

or
g solute mg solute
ppm = ×106 ppm =
mL solution L solution

6.75 g 6 6.75 g  1000

1 g 
mg

ppm = ×10 ppm =

2.5×106 L  1000
1 L 
mL
2.5×106 L

ppm = 0.0027 ppm = 0.0027

 ppm & ppb
Example Problem 2
An Olympic sized swimming pool contains 2,500,000 L of
water. If 1 tsp of salt (NaCl) is dissolved in the pool, what is
the concentration in ppb?

1 teaspoon = 6.75 g NaCl

or
g solute  g solute
ppb = ×109 ppb =
mL solution L solution

ppb =
6.75 g
×10 9
ppb =
6.75 g  106 mg
1 g 
2.5×106 L  1000
1 L 
mL
2.5×106 L
ppb = 2.7 ppb = 2.7
 Mole Fraction
B A
A B
A A
A B

B A B A A
A

Mole Fraction (c)

moles of A A
c A = sum of moles of all components A + B

moles of B B
c B = sum of moles of all components A + B

Since A + B make up the

entire mixture, their mole
fractions will add up to one.
 A  B  1.00
 Mole Fraction
Example Problem 1
In our glass of iced tea, we have added 3 tbsp of sugar (C12H22O11).
The volume of the tea (water) is 325 mL. What is the mole fraction
of the sugar in the tea solution?
(1 tbsp sugar ≈ 25 g)

First, we find the moles of both the solute and the

solvent.

 1 mol C12 H 22 O11   1 mol H 2 O 

75.g C12 H 22O11   = 0.219 mol 325mL H 2 O   = 18.1 mol
 342 g C12 H 22 O11   18.0 g H 2 O 
Next, we substitute the moles of both into the mole fraction equation.

χ sugar =
moles solute
total moles solution
=
0.219 mol sugar
(0.219 mol + 18.1 mol)
 0.012
 Mole Fraction
Example Problem 2
Air is about 78% N2, 21% O2, and 0.90% Ar.
What is the mole fraction of each gas?

First, we find the moles of each gas. We assume 100.

grams total and change each % into grams.
 1 mol N 2   1 mol O 2 
78g N 2   = 2.79 mol 21g O 2   = 0.656 mol
 28 g N 2   32 g O 2 
 1 mol Ar  Next, we substitute the moles of each into the
0.90g Ar   = 0.0225 mol
 40. g Ar  mole fraction equation.

χ =
moles N 2
N2 total moles χ =
moles O 2
O2 total moles χ Ar =
moles Ar
total moles
2.79 mol N 2 0.656 mol O 2 0.0225 mol Ar
= = =
(2.79 + 0.656 + 0.0225) (2.79 + 0.656 + 0.0225) (2.79 + 0.656 + 0.0225)

 0.804  0.189  0.00649

SAMPLE EXERCISE 13.4 Calculation of Mass-Related Concentrations
(a) A solution is made by dissolving 13.5 g of glucose (C6H12O6) in 0.100 kg
of water. What is the mass percentage of solute in this solution? (b) A 2.5-g
sample of groundwater was found to contain 5.4g of Zn2+ What is the
concentration of Zn2+ in parts per million?

PRACTICE EXERCISE
(a)Calculate the mass percentage of NaCl in a solution containing 1.50 g of
NaCl in 50.0 g of water. (b) A commercial bleaching solution contains 3.62
mass % sodium hypochlorite, NaOCl. What is the mass of NaOCl in a bottle
containing 2500 g of bleaching solution?

PRACTICE EXERCISE
A commercial bleach solution contains 3.62 mass % NaOCl in water.
Calculate (a) the molality and (b) the mole fraction of NaOCl in the solution.
PRACTICE EXERCISE
(a) Calculate the mass percentage of NaCl in a solution containing 1.50 g of NaCl in 50.0 g of water. (b) A
commercial bleaching solution contains 3.62 mass % sodium hypochlorite, NaOCl. What is the mass of NaOCl
in a bottle containing 2500 g of bleaching solution?

Answers: (a) 2.91%, (b) 90.5 g of NaOCl

Answers: (a) 0.505 m, (b) 9.00  10–3

 Preparation of Solutions
• Now that you know how to calculate M, n and
v, what does that mean?
• You can make your own solutions!
• What are the steps in making a proper
solution?
Preparation of Solutions
 Concentration of Solutions
• How many grams of Potassium Dichromate, K2Cr2O7, are required to prepare a 250mL
solution with a concentration of 2.16M?

250mL x 1L/ 1000mL = .250L

M= n/v
n= M x v
n= 2.16M x .250L
n= 0.54 mol

moles = g/MW
Grams = moles x MW
Grams = 0.54 mol K2Cr2O7 x 294.2 g K2Cr2O7
Grams = 159

159 grams of K2Cr2O7 are needed to prepare the requested solution.

 Concentration of Solutions
• In a biochemical assay, a chemist needs to add 0.381g of glucose to a reaction
mixture. Calculate the volume in millimeters of a 2.53M glucose solution that she
should use for this addition.

moles = g/MW
moles = 0.381g C6H12O6/ 180.2g C6H12O6
moles = 2.114 x 10 –2 mol C6H12O6

M = n/v
v = n/M
v = 2.114 x 10 –2 mol C6H12O6 / 2.53M C6H12O6
v = 8.36mL

She should use 8.36mL of the 2.53M glucose solution.

 Preparation of Solutions
• Explain the process of creating 1L of 3.0M KCl.
M = n/v
n=Mxv
n = 3.0M x 1L
n = 4.0 mol of KCl needed

moles= g/MW
Grams = moles x MW
Grams = 4.0 mol KCl x 36.0g KCl
Grams = 144g KCl

Weigh out 144g of KCl. Put in a 1L flask. Add enough dH20 to dissolve
KCl. Fill flask to 1L meniscus.
 Dilution of Solutions
• Dilution- the procedure for preparing a less
concentrated solution from a more concentrated
one.
• Dilutions can be made in increments of 10, 20, 50 or
any other value.
• Serial Dilution- the process of diluting a solution by
removing part of it, placing this in a new flask and
adding water to a known volume in the new flask.
 Dilution of Solutions
• When you want to dilute a solution, what
happens to the number of moles present in
the solution?
– Do they increase?
– Decrease?
– Stay the same?
Dilution of Solutions
Dilution of Solutions
 Dilution of solutions
• Since moles are constant before and after
dilution, we can use the following formula for
calculations.

• MiVi = MfVf
Solubility Product Constant

Ksp
 Ksp, the solubility-product constant.
An equilibrium can exist between a partially soluble substance and its
solution:

                                                                             
 For example:
BaSO4 (s)  Ba2+ (aq) + SO42- (aq)
• When writing the equilibrium constant expression for
the dissolution of BaSO4, we remember that the
concentration of a solid is constant.

The equilibrium expression is therefore:

K = [Ba2+][SO42-]

K = Ksp, the solubility-product constant.

Ksp = [Ba2+][SO42-]
 The Solubility Expression

AaBb(s)  aAb+ (aq) + bBa- (aq)

Ksp = [Ab+]a [Ba-]b

Example: PbI2 (s)  Pb2+ + 2 I-

Ksp = [Pb2+] [I-]2
The greater the ksp the more soluble the solid
is in H2O.
 Solubility and Ksp
Three important definitions:
1) solubility: quantity of a substance that
dissolves to form a saturated solution
2) molar solubility: the number of moles of the
solute that dissolves to form a liter of
saturated solution
3) Ksp (solubility product): the equilibrium
constant for the equilibrium between an
ionic solid and its saturated solution
 Calculating Molar Solubility
Calculate the molar solubility of Ag2SO4 in one
liter of water. Ksp = 1.4 x 10-5
Ag2SO4 2Ag+ + SO42-
Initial 0 0
Change +2x +x
Equilb 2x x

Ksp = [Ag+]2[SO42-] = (2x)2(x)= 1.4 x 10-5

X = 1.5 x 10-2 mol Ag2SO4 /L (molar solubility)
 Common ion Effect
PbI2(s) Pb2+(aq) + 2I–(aq)

Common ion: “The ion in a mixture of ionic

substances that is common to the
formulas of at least two.”

Common ion effect: “The solubility of one

salt is reduced by the presence of another
having a common ion”
 Example #1

What is the Molar solubility of PbI2 if the concentration

of NaI is 0.10? Ksp = 7.9 x 10–9
So [I-] = 0.10 M
PbI2(s) Pb2+(aq) I –(aq)
R 1 2
I 0 0.10
C x 2x
E x 0.10 + 2x
Ksp = [Pb2+(aq)] [I –(aq)]2
Ksp = [x] [0.10 + 2x]2 = 7.9 x 10–9
x is small, thus we can ignore 2x in 0.10 + 2x
Ksp = [x] [0.10]2 = 7.9 x 10–9 , x = 7.9 x 10–7 M
 Common Ion Effect
• Thus the solubility of the PbI2 is reduced by
the presence of the NaI.

Ksp of PbI2 = 7.9 x 10-9, so the molar solubility is

7.9 x 10-9 = (x)(2x)2 = 4x3
X = 1.3 x 10-3
Which is much greater than 7.9 x 10-7 when 0.10
M NaI is in solution.
 Example #2

Molar solubility of AgI? Ksp = 8.3 x 10–17

Concentration of NaI is 0.20, thus [I–] = 0.20

AgI(s) Ag+(aq) I –(aq)

R 1 1
I 0 0.20
C x x
E x 0.20 + x
Ksp = [Ag+(aq)] [I –(aq)]
Ksp = [x] [0.20 + x] = 8.3 x 10–17
x is small, thus we can ignore it in 0.20 + x
Ksp = [x] [0.20] = 8.3 x 10–17, x = 4.2 x 10–16
 Common Ion Effect
• When two salt solutions that share a common
ion are mixed the salt with the lower ksp will
precipitate first.
Example: AgCl ksp = [Ag+][Cl-] = 1.6 x10-10
[Ag+][Cl-] = 1.6 x 10-10
X2 = 1.6 x 10-10
X = [Ag+] = [Cl-] = 1.3 x 10-5 M
 Common Ion Effect
Add 0.10 M NaCl to a saturated AgCl solution.
[Cl-] = 0.10 (common ion)
[Ag+][Cl-] = 1.6 x 10-10
[Ag+][0.10 + x] = 1.6 x 10-10 (x is small)
[Ag+]= 1.6 x 10-10/ 0.10 M
[Ag+]= 1.6 x 10-9
 [Ag+] = 1.3 x 10-5 from the previous slide

So, some AgCl will precipitate when the NaCl is added

because the molar solubility of the solution is now
less than the that of AgCl alone.
 Will a Precipitation Occur?
If 1.00 mg of Na2CrO4 is added to 225 ml of 0.00015 M
AgNO3, will a precipitate form?
Ag2CrO4 (s)  2Ag+ + CrO42-

Determine the initial concentration of ions. Ag+ = 1.5

x 10-4
CrO42- = 1.00 x 10-3 g / MM = 6.17 x 10-6 mol CrO42-/ .225
L = 2.74 x 10-5 M
 Will a Precipitation Occur?
• Compare the initial concentration to the
solubility product constant
Initial concentration of ions: (Ag+)2 (CrO42-)
(1.5 x 10-4)2 (2.74 x 10-5 M)= 6.2 x 10-13
Ag2CrO4 Ksp = 1.1 x 10-12

• No precipitation will occur because the initial

concentration is less than the Ksp.
 Predicting if Precipitation Occurs

Step 1: write the balanced equilibrium:

Ag2CrO4(s)  2Ag+(aq) + CrO42–(aq)

Step 2: Write the Ksp equation:

Ksp = [Ag+]2[CrO42–] = 1.2 x 10–12

Step 3: Determine the initial concentration of ions

[Ag+]2[CrO42–] = [4.8 x 10–5]2[3.4 x 10–4]
= 7.8 x 10–13
ion product is less than Ksp, thus no precipitate will form
(more could be dissolved)
 Formation Constants
for Complex Ions
• Kform = [Cu(NH3)42+]
[Cu2+][NH3]4
The solution of a slightly soluble salt increase when
one of its ions can be changed to a soluble
complex ion.
AgBr (s) Ag+ + Br - Ksp = 5.0 x 10-13

Add NH3
Ag+ + 2NH3 Ag(NH3)2+ kform = 1.6 x 107
 Formation Constants
for Complex Ions
• The very soluble silver complex ion removes Ag+
from the solution and shifts the equilibrium to the
right increasing the solubility of AgCl.
AgBr + 2NH3 Ag(NH3)2+ + Br -
Kc = 8.0 x 10-6 = [Ag(NH3)2+][Br -]
[NH3]

Kc = kform x ksp = (1.6 x 107)(5.0x10-13)

= 8.0 x 10-6
 Example
• How many moles of AgBr can dissolve in 1 L of
1.0 M NH3?
AgBr + 2NH3 Ag(NH3)2+ + Br –
1.0 0 0
-2x +x +x
1.0-2xx x
Kc = x2
(1.0-2x)2 = 8.0x10-6
X = 2.8x10-3, 2.8 x 10-3 mol of AgBr dissolves in 1L of
NH3