CHEM 1011

General Chemistry A: Property of Solutions

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Reactions, Thermodynamics, (Textbook Ch. 10)
and Reaction Kinetics

2024 Fall Semester 2024-09-12

 Review of Last Lecture

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3

Colligative Properties
 Freezing Point Depression
• Nonvolatile solute lowers the freezing point of
the solvent. c.f. boiling point elevation
𝚫𝑻 = 𝑲𝒃 𝒎𝒔𝒐𝒍𝒖𝒕𝒆
𝚫𝑻 = 𝑲𝒇 𝒎𝒔𝒐𝒍𝒖𝒕𝒆
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• ΔT = freezing-point depression
• Kf = molal freezing-point depression constant
• msolute = molality of solute
 Molal Freezing-Point Depression Constants
ΔT = Kfmsolute

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Note that
the unit
is again
the reciprocal
of molal
 De-icing

More NaCl is used in de-icing than in food processing

 Anti-freeze
• Salt is bad for engines
• Use ethylene glycol instead
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– High boiling (non-volatile) liquid
– Colligative effect
 A harder example
• You take 20.0 g of a sucrose (C12H22O11) and NaCl
mixture and dissolve it in 1.0 L of water. The
freezing point of this solution is found to be -
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0.426 C. Assuming ideal behavior, calculate the
mass percent composition of the original
mixture, and the mole fraction of sucrose in the
original mixture.
 Breaking down to steps
(1) Freezing point depression
𝚫𝑻 = 𝑲𝒇 𝒎𝒔𝒐𝒍𝒖𝒕𝒆
is dependent on molality

𝒎𝒐𝒍𝒆𝒔 𝒐𝒇 𝒔𝒐𝒍𝒖𝒕𝒆
𝒎𝒔𝒐𝒍𝒖𝒕𝒆 = (2) Molality is dependent
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𝒌𝒈 𝒐𝒇 𝒔𝒐𝒍𝒗𝒆𝒏𝒕 on moles of solute

(3) Moles can be calculated

𝒎𝒐𝒍𝒆𝒔 𝒐𝒇 𝒔𝒐𝒍𝒖𝒕𝒆 = 𝒎𝒐𝒍𝒆𝒔 𝒐𝒇 𝒔𝒖𝒄𝒓𝒐𝒔𝒆 from the sum of components
+𝒎𝒐𝒍𝒆𝒔 𝒐𝒇 𝑵𝒂+ + 𝒎𝒐𝒍𝒆𝒔 𝒐𝒇 𝑪𝒍− (Na+ and Cl- should be treated
SEPARATELY)
 0.426 = 1.86 × msolute msolute = 0.23 mol/kg

w/58.5 + w/58.5 + (20-w)/342 = 0.23 w = 5.5 g

Na+ Cl- sucrose

5.5/20 = 0.275 = 27.5%

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The mixture is 72.5% sucrose and 27.5% sodium chloride.

5.5/58.5 = 0.094 mol NaCl 0.042 / (0.042 + 0.094) = 0.309

14.5/342 = 0.042 mol sucrose
The mole fraction of the sucrose is 0.309.
Note: To solve this problem, the students must assume
that i = 2 for NaCl.
 Combining Both Effects
• Introducing non-volatile solute increases the
liquid range
Freezing point Boiling point
11 of solvent of solvent

Freezing point Boiling point

of solution of solution
 Osmosis
• Flow of solvent into the solution through a
semipermeable membrane
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Time Time
 Why osmosis?
• First imagine the situation with no membrane

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(3) The concentration (2) The concentration
(molarity) on the left (molarity) on the right
will increase will decrease
X
(1) The solute will slowly
diffuse from right to left
 Putting in the semi-permeable membrane
(2) The two sides still have
the tendency to equalize
their concentrations

(5) The water level

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(3) The concentration on the right will rise,
(molarity) on the left at the same time
cannot change the concentration
(molarity) on the right
(4) But water can still will decrease
pass though the
semi-permeable
membrane
X
(1) The solute CANNOT
diffuse from right to left
 Osmotic Pressure

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Extra pressure is needed

to counteract the “upward
pushing pressure”
The end with higher
(osmotic pressure)
concentration (molarity)
of the solution if we want
will “push” upwards
to maintain the water level
 Osmosis in Cells Buffered isotonic solution

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Hypotonic soln. Isotonic soln. Hypertonic soln.

(soln. w/ lower (soln. w/ equal (soln. w/ higher
osmotic pressure) osmotic pressure) osmotic pressure)
 Osmotic pressure
Π = 𝑀𝑅𝑇
• Π = osmotic pressure (atm)
17 • M = molarity of the solution
• R = gas law constant
• T = temperature (Kelvin)
 Example
• A plant cell has a natural concentration of 0.25
m. You immerse it in an aqueous solution with a
freezing point of –0.246 C.
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• Will the cell explode, shrivel, or do nothing?
 Answer

0.246 = 1.86 × msolute msolute = 0.132 mol/kg

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The cell will explode (or at least expand). The concentration of
the solution is 0.132 m. Thus, the cell has a higher
concentration, and water will enter the cell.
 Example
• When 33.4 mg of a compound is dissolved in
10.0 mL of water at 25 C, the solution has an
osmotic pressure of 558 torr. Calculate the
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molar mass of this compound.
 Answer
 = MRT R = 0.08206 L atm / K mol
Mind the units!!!
558/760 = 0.734 atm
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M = 0.734 / (0.08206×298) = 0.03 mol/L

33.4
10.0 ≈ 0.03 x = 111 g/mol
x
22 dialysis: 透析; 洗腎
Dialysis involves elimination of waste
matter from the blood and maintaining
electrolyte balance through osmosis.
Dialysis membrane allows passage of solvent and small solute molecules/ions:
In kidney dialysis, the dialyzing solution contains the same concentrations
of ions and small molecules as blood but has none of the waste products
normally removed by the kidneys, so waste molecules migrate into dialyzing solution.
 Revisiting our challenging example
• You take 20.0 g of a sucrose (C12H22O11) and NaCl
mixture and dissolve it in 1.0 L of water. The
freezing point of this solution is found to be -
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0.426 C. Assuming ideal behavior, calculate the
mass percent composition of the original
mixture, and the mole fraction of sucrose in the
original mixture.
 Breaking down to steps
(1) Freezing point depression
𝚫𝑻 = 𝑲𝒇 𝒎𝒔𝒐𝒍𝒖𝒕𝒆
is dependent on molality

𝒎𝒐𝒍𝒆𝒔 𝒐𝒇 𝒔𝒐𝒍𝒖𝒕𝒆
𝒎𝒔𝒐𝒍𝒖𝒕𝒆 = (2) Molality is dependent
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𝒌𝒈 𝒐𝒇 𝒔𝒐𝒍𝒗𝒆𝒏𝒕 on moles of solute

(3) Moles can be calculated

𝒎𝒐𝒍𝒆𝒔 𝒐𝒇 𝒔𝒐𝒍𝒖𝒕𝒆 = 𝒎𝒐𝒍𝒆𝒔 𝒐𝒇 𝒔𝒖𝒄𝒓𝒐𝒔𝒆 from the sum of components
+𝒎𝒐𝒍𝒆𝒔 𝒐𝒇 𝑵𝒂+ + 𝒎𝒐𝒍𝒆𝒔 𝒐𝒇 𝑪𝒍− (Na+ and Cl- should be treated
SEPARATELY)
 Think carefully
• What is the molality of solute when 0.04 moles
of sucrose is dissolved in 1kg of water?
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0.04 m
sucrose
solution
 Recall
• What is the molality of solute when 0.03 moles
of NaCl is dissolved in 1kg of water? Particle
conc. = 0.06 m
26 (NOT 0.03 m)

???
 0.426 = 1.86 × msolute msolute = 0.23 mol/kg

w/58.5 + w/58.5 + (20-w)/342 = 0.23 w = 5.5 g

Na+ Cl- sucrose

5.5/20 = 0.275 = 27.5%

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The mixture is 72.5% sucrose and 27.5% sodium chloride.

5.5/58.5 = 0.094 mol NaCl 0.042 / (0.042 + 0.094) = 0.309

14.5/342 = 0.042 mol sucrose
The mole fraction of the sucrose is 0.309.
Note: To solve this problem, the students must assume
that i = 2 for NaCl.
28

van 't Hoff Factor

 Motivation
• Moles of dissolved particles in the solution are
not necessarily equal to the moles of solute
0.03 moles of NaCl
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0.06 moles of
dissolved particles
(NOT 0.03 m)
 van 't Hoff Factor
𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝑝𝑎𝑟𝑡𝑖𝑐𝑙𝑒𝑠 𝑖𝑛 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛
• van 't Hoff Factor 𝑖 =
𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑒 𝑑𝑖𝑠𝑠𝑜𝑙𝑣𝑒𝑑

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• The expected value for i can be determined for a
salt by noting the number of ions per formula unit
– NaCl (i = 2)
– KNO3 (i = 2)
– Na3PO4 (i = 4)
 Are these situations possible?

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 “Effective Number of Solutes”
• “Number of solute” is the key
for colligative properties
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• But electrolytes do not always

fully dissociate
– Ion Pairing
– Smaller “effective number”
 Ion Pairing
• Most important in concentrated solutions.
– As the solution becomes more dilute, the ions are
farther apart and less ion pairing occurs.
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• Occurs to some extent in all electrolyte
solutions.
• Most important for highly charged ions.
 Examples of van 't Hoff Factors

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+1, -1
+2, -1
+2, -2
+3, -1
+1, -1
 Example
• For a binary salt MX that dissociates in water
into M+ and X-, we found that a 0.1 m (molal)
solution of MX has a freezing point of −0.335℃,
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– What is the van 't Hoff factor of MX at the stated
condition?
– What is the percentage of dissociation?
 Answer

• 𝚫𝑻 = 𝒊𝑲𝒇 𝒎𝒔𝒐𝒍𝒖𝒕𝒆
# of MX units = 5
• (0.335) = i (1.86) (0.1) # of M+ = 4

36 • i (van 't Hoff factor) = 1.8 # of X- = 4

# of undissoc. MX = 1

• Percentage dissociation
= 80% 2*x + (1-x) = 1.8
 Modifying the Equations
• Boiling point elevation
Δ𝑇 = 𝑖𝐾𝑏 𝑚𝑠𝑜𝑙𝑢𝑡𝑒
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• Freezing point depression
Δ𝑇 = 𝑖𝐾𝑓 𝑚𝑠𝑜𝑙𝑢𝑡𝑒
• Osmotic pressure
Π = 𝑖𝑀𝑅𝑇
38

Colloid
 Definition of Solution
• A solution is a homogeneous type of mixture of
two or more substances. A solution has two
parts: a solute and a solvent. The solute is the
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substance that dissolves, and the solvent is the
majority of the solution
 Colloid
• A suspension of tiny particles in some medium.

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• Suspended particles are single large molecules
or aggregates of molecules or ions ranging in
size from 1 to 1000 nm.
c.f. Length of chemical bond ~ 0.1 nm
Wavelength of visible light ~ 500 nm

• Characterized by Tyndall effect

 Tyndall Effect
• Scattering of light
by particles
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 Examples of Colloids

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