NON-IDEAL SYSTEMS ACTIVITY (a)

Comparison between Ideal and Non-ideal systems:

IDEAL NON-IDEAL - “effective” mole fraction or concentration
- gases obey PV = nRT - both gases and solutions - a dimensionless quantity that is equal to unity if
- solutions follow Raoult’s deviate from ideal behavior the substance is in its standard state
law classified as (+) or (-)
- chemical potential (µ)of deviating - Each measure of the activity corresponds to a
component i in a mixture is - Chemical potential is different standard state.
defined in terms of mole measured in terms of
fraction (𝜒): activity (a)

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Reference: Atkins, P. W., De Paula, J., & Keeler, J. (2018). Atkins' physical chemistry. Oxford university press.

Activity of component i in solution: SUMMARY OF PROPERTIES

where: 𝑎𝑖 = activity of I IDEAL NON-IDEAL

𝛾𝑖 = activity coefficient of i

Raoult’s Law
𝑚 = molality of solution
𝑃𝐴 = 𝜒𝐴 𝑃𝐴° 𝑃𝐴 = 𝑎𝐴 𝑃𝐴°
Type of solutions 𝑃𝐵 = 𝜒𝐵 𝑃𝐵° 𝑃𝐵 = 𝑎𝐵 𝑃𝐵°
NON-IDEAL: Positively deviating behavior 𝛾>1 𝑎>𝑚
Henry’s Law 𝑃𝐵 = 𝜒𝐵 𝐾𝐵 𝑃𝐵 = 𝑎𝐵 𝐾𝐵
NON-IDEAL: Negatively deviating behavior 𝛾<1 𝑎<𝑚
IDEAL 𝛾=1 𝑎=𝑚 Vapor Pressure Δ𝑃 = 𝑃𝐴 − 𝑃𝐴° Δ𝑃 = 𝑃𝐴 − 𝑃𝐴°

Lowering
Δ𝑃 = 𝜒𝐵 𝑃𝐴° Δ𝑃 = 𝑎𝐵 𝑃𝐴°
DILUTE 𝛾→1 𝑎→𝑚
𝐴 = 𝑠𝑜𝑙𝑢𝑡𝑒; 𝐵 = 𝑠𝑜𝑙𝑣𝑒𝑛𝑡
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 SUMMARY OF PROPERTIES (cont…) Types of Non-Ideal Solutions
IDEAL NON-IDEAL
1. Non-electrolytic solution
Freezing Point ഥ 1 1
∆𝑓𝑢𝑠 𝐻 ഥ 1 1
∆𝑓𝑢𝑠 𝐻 - uncharged molecules in solution
Depression 𝑙𝑛𝜒𝐴 = − 𝑙𝑛𝑎𝐴 = −
- solute is non-electrolyte, can be volatile or not
𝑅 𝑇𝑓° 𝑇𝑓 𝑅 𝑇𝑓° 𝑇𝑓

Boiling Point ഥ 1
∆𝑣𝑎𝑝 𝐻 1 ഥ 1
∆𝑣𝑎𝑝 𝐻 1 2. Electrolytic solution
Elevation - presence of ions in solution
𝑙𝑛𝜒𝐴 = − ° 𝑙𝑛𝑎𝐴 = − °
𝑅 𝑇𝑏 𝑇𝑏 𝑅 𝑇𝑏 𝑇𝑏

Osmotic −𝜋𝑉ത𝐴° −𝜋𝑉ത𝐴°

- Solute (non-volatile) is either strong or weak
Pressure
𝑙𝑛𝜒𝐴 =
𝑅𝑇
𝑙𝑛𝑎𝐴 =
𝑅𝑇 electrolyte
𝐴 = 𝑠𝑜𝑙𝑢𝑡𝑒; 𝐵 = 𝑠𝑜𝑙𝑣𝑒𝑛𝑡
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Electrolytic solution Electrolytic solutions

- more non-ideal than non-electrolytic solutions 1. Strong Electrolytes
Illustration:
0.005 m C6H12O6 vs. 0.005 m NaCl - complete dissociation (100%)
(non-electrolyte) (strong electrolyte) - ex. strong acids, strong bases and ionic salts
- in 1 kg water, C6H12O6 solution produces 0.005 mole of 2. Weak Electrolytes
C6H12O6 - does not completely dissociates
- in 1 kg water, NaCl solution produces 0.001 mole of solute - ex. weak acids, weak bases and slightly soluble
(0.005 Na+ + 0.005 Cl-, more concentrated, more non-ideal)
- The lower the amount of solute, activity ≈molality (𝛾 → salts
1; 𝑎 → 𝑚) (see slide 3)
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Activities for Electrolyte Solutions Activities for Electrolyte Solutions
mean ionic activity coefficient 𝛾±
activity of the 𝑎 = 𝛾𝑚 𝜇 = 𝜇° + 𝑅𝑇𝑙𝑛𝑎 mean ionic molality 𝑚±
electrolyte 1ൗ
𝑚± = 𝜈+ 𝜈+ 𝜈− 𝜈− 𝜈𝑚
activity of cation 𝑎+ = 𝛾+ 𝑚+ ° + 𝑅𝑇𝑙𝑛𝑎
𝜇 + = 𝜇+ +
Useful Relations: Note:
activity of anion 𝑎− = 𝛾− 𝑚− ° + 𝑅𝑇𝑙𝑛𝑎
𝜇 − = 𝜇− −
𝑎 = 𝑎± 𝜈 ν = # of moles of ions produced
in the solution
𝑎± 𝜈 = 𝑎+ 𝜈+ 𝑎− 𝜈−
mean ionic
ν+ = # of moles of cations
𝑎± 𝜈 = 𝛾± 𝜈 𝑚± 𝜈 produced from 1 mole of
° electrolyte
𝑎± = 𝛾± 𝑚± 𝜇± = 𝜇± + 𝑅𝑇𝑙𝑛𝑎± 𝑎 = 𝛾± 𝜈 𝜈+ 𝜈+ 𝜈− 𝜈− 𝑚𝜈
activity* 𝑎 = 𝛾± 𝜈 (𝜈+ 𝑚+ )𝜈+ (𝜈− 𝑚− )𝜈−
ν-= # of moles of anions

*geometric mean of the individual ion activities

produced from 1 mole of
electrolyte

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Sample Problem Debye-Hückel Theory

1.1. Determine the equations for m+ and a in terms - devised by Peter Debye and Erich Hückel in 1923
of m for: - explains the unexpected behavior of electrolyte
solutions by accounting for their electrostatic
a. NaCl interactions
b. Na2SO4 - Ions tend to cluster around opposite charge
c. Ca3(PO4)2 ions i.e. tendency for anions to be found
around cations, and vice versa
- Due to long range and strength of the
Coulombic interaction between ions
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Photo: Atkins, P. W., De Paula, J., & Keeler, J. (2018). Atkins' physical chemistry. Oxford university press.
DEBYE-HÜCKEL LIMITING LAW
IONIC STRENGTH
(DHLL)
𝑙𝑜𝑔𝛾± = 𝐴(𝑧+ )(𝑧− ) 𝐼 1
𝐼 = ෍ 𝑐𝑖 𝑧𝑖 2
2
where: A = 0.509 for aqueous solution at 25 °C
z+ = charge of cation where ci = concentration of ion i
z- = charge of anion zi = ionic charge of ion i
I = ionic streng
- emphasizes charges of the ions since charge #s occur
- permits to calculate activity coefficient of ions from as squares
their charge and their average size - ↑zi ↑I ↓γ ↓a ↑non-ideal
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Determination of activity coeffcient

Sample Problem
(𝜸± )
1. Debye-Hückel Limiting Law (I < 0.01) 1.2. At 25 °C estimate the mean activity
𝑙𝑜𝑔𝛾± = 0.509(𝑧+ )(𝑧− ) 𝐼
coefficient, γ+ and the activity, a, of
2. Extended Debye-Hückel Law (I = 0.01 to 0.1) a. 0.005 m KCl (aq)
𝑙𝑜𝑔𝛾± =
𝐴(𝑧+ )(𝑧− ) 𝐼
1+𝐵 𝐼
b. 0.005 m Ca(NO3)2 (aq)
3. Davies Equation (I > 0.1)
𝐼
𝑙𝑜𝑔𝛾± = 0.509(𝑧+ ) 𝑧− − 0.301𝐼
1+ 𝐼

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WEAK ELECTROLYTES
1. Equilibrium in slightly soluble salts:
Consider salt AX3:
𝐴𝑋3(𝑠) ⇌ 𝐴3+ 𝑎𝑞 + 3𝑋 −
- Solubility product constant:
3
𝐾𝑠𝑝 = (𝑎𝐴3+ )(𝑎𝑋 − ) = 𝑎𝐴𝑋3
- RECALL: (Slide 10) 𝑎 = 𝑎± 𝜈
𝑎± 𝜈 = 𝑎+ 𝜈+ 𝑎− 𝜈−
𝑎± 𝜈 = 𝛾± 𝜈 𝑚± 𝜈
𝑎 = 𝛾± 𝜈 𝜈+ 𝜈+ 𝜈− 𝜈− 𝑚𝜈
WEAK ELECTROLYTES
1. Equilibrium in slightly soluble salts:
SALTING-IN EFFECT
𝑎𝑞
- increased in solubility in the presence of inert ion
COMMON-ION EFFECT
- decrease in solubility due to presence of common
ion
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Sample Problem WEAK ELECTROLYTES

2. Equilibrium in weak acids:
1.3. The Ksp of AgBr at 25 °C is 7.7x10-13. Calculate the - Consider weak acid HA:
solubility of AgBr in
a. H2O
𝐻𝐴(𝑎𝑞) + 𝐻2 𝑂(𝑙) ⇌ 𝐻3 𝑂+ (𝑎𝑞) + 𝐴− 𝑎𝑞

b. 0.01 m NaCl 𝐾𝑎 =
(𝑎𝐻3𝑂+ )(𝑎𝐴− )

c. 0.01 m NaBr
𝑎𝐻𝐴
- RECALL: (slide 3)
DILUTE: 𝛾 → 1; 𝑎 → 𝑚

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Sample Problem COLLIGATIVE PROPERTIES OF
ELECTROLYTIC SOLUTIONS
1.4. Calculate the pH of 0.01 m HCN solution at 25 °C van’t Hoff factor, i
(Ka = 2.1x10-9) in - the measure of effect of solute on colligative properties
a. H2O - ratio between the actual concentration of particles produced when
b. 0.01 m NaCl the substance is dissolved, and the concentration of a substance as
c. 0.01 m CaCl2 calculated from its mass
- For most non-electrolytes: i = 1
- For most ionic compounds: i = equal to the number of
discrete ions in a formula unit of the substance
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COLLIGATIVE PROPERTIES
van’t Hoff factor, i
(Equations)
1. Strong electrolytes 𝑖≅𝜈
2. Weak electrolytes VP Lowering 𝑃𝐴° − 𝑃𝐴 = 𝜒𝐵 𝑃𝐴°
𝑖𝑛𝐵
°
a. when solute particles dissociate in 𝑃𝐴 − 𝑃𝐴 = 𝑃𝐴°
𝑖−1 𝑖𝑛𝐵 + 𝑛𝐴
solution (i > unity) (Ex. AgBr in water) 𝛼=
FP Depression
ν−1
Δ𝑇𝑓 = 𝑖𝐾𝑓 𝑚
b. when solute particles associate in
BP Elevation
𝑖−1
solution (i <unity) (Ex. Benzoic acid in 𝛼=
1 Δ𝑇𝑏 = 𝑖𝐾𝑏 𝑚
benzene, ethanoic acid in benzene) −1
Osmotic Pressure
𝜈
π = 𝑖𝑀𝑅𝑇
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Sample Problem:

1.5. Assuming 100 % dissociation, calculate the freezing

point and boiling point of a 0.01m MgBr2. (for H2O:
Kb = 0.56 °C-kg/mol; Kf = 1.86 °C-kg/mol )
1.6. Calculate the Ka of tartaric acid if a 0.100 m aqueous
solution freezes at -0.205°C. Assume that only the
first ionization is important.(Kf = 1.86 °C-kg/mol )

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