Chemical Thermodynamic-7-2017

HÓA LÝ 1:
NHIỆT ĐỘNG HÓA HỌC

(Chemical thermodynamic)
MSHP: KC112
CBGD: Lương Huỳnh Vủ Thanh
1
Chương 6 Dung dịch và cân bằng dung dịch - hơi
6.1 Đại cương về dung dịch
In chemistry, a solution is a homogeneous mixture composed of
only one phase. In such a mixture, solute(s) are a substances
dissolved in another substance, known as a solvent.
In this chapter, solvent is signed as 1 and solute is signed as i = 2,
3, 4, etc. It only concerns solution of gas in liquid, liquid in
liquid, and equilibrium of liquid and its vapor.
Concentration Formula
Percentage (%) C%2 = (g2/g1+g2+…)x100%
Molar (M, mol/L) CM2 = n2/V
Equivalent (N, eqv. g/L) CN2 = neqv2/V
2
Molality (m, mol/1000g) Cm2 = (n2/msol)x1000
Mole fraction x2 = n2/ 𝑛𝑖 and 𝑥𝑖 = 1
An appropriate type of concentration can be chosen based on
experimental condition and purpose of research.
In industry, C% is normally used, meanwhile CM is used in
kinetics of chemical reaction and theory of chemical equilibrium.
In the same time, analytical chemistry and quantifiable calculation
commonly apply equivalent concentration; molality concentration
is utilized for calculation in electrochemistry and theory of
thermodynamics.
All types of concentration are related to each other.
𝑀1 .𝐶𝑚2 3
Ex: CN = n.CM; x2 =
1000+𝑀1 .𝐶𝑚2
There are several ways to categorize solution, it is up to
research purpose. In thermodynamics, solution can be divided into
three types: ideal solution, infinite dilute solution and real solution
a. Dung dịch lý tưởng
Ideal solution is solution in which its physical and chemical
natures are the same. The strength of interaction among different
molecules is equal. fA-A = fB-B = fC-C.
∆U = 0; ∆H = 0; ∆U = 0; ∆G < 0; ∆S > 0
μi = μi* (T) + RTlnxiL
4
Generally speaking, there are rare solutions considered as ideal
solutions, namely solution of homologous series or of isomerism.
b. Dung dịch vô cùng loãng
It is a solution of very less solute and much more solvent. It
means that x1 → 1 and xi → 0.
As concentration of solution is infinite dilute, properties of
constituents all follow laws of ideal solution such as Henry’s law,
Raoult’s law. Chemical potential in this case also obeys following
eq. μi = μi* (T) + RTlnxiL.
c. Dung dịch thực
Real solution is solution in which the strength of interaction
among different molecules is different from. fA-A ≠ fB-B ≠ fC-C.
5
∆U ≠ 0; ∆H ≠ 0; ∆U ≠ 0; μi = μistd (T) + RTlnai
6.2 Sự hòa tan của khí trong chất lỏng
Solubility of gas in liquid is complicated, but generally there
are two main parameters affecting the solubility of gas in liquid,
namely temperature and pressure.
In terms of Gibbs phase rule, c = k – f + 2 = 2 – 2 + 2 = 2.
Thus, x2 = f(T,P).
If T = const. → x2 = f(P); If P = const. → x2 = f(T)
6
a. Ảnh hưởng của áp suất đến độ tan của các khí trong chất lỏng
7
At a constant temperature, the amount of a given gas that
dissolves in a given type and volume of liquid is directly
proportional to the partial pressure of that gas in equilibrium with
that liquid.
xi = kH . Pi
where kH is Henry’s constant. It depends on T and solvent’s
nature, but not on P.
μi (gas) = μi (liquid) → μi°(T) + RTlnPi = μi*(T) + RTlnxi
→ ln (xi/Pi) = (μi° - μi*)/RT 8
The right side of eq. depends on T only and it signed as lnkH.

So ln (xi/Pi) = ln kH → xi/Pi = kH. Henry’s law can apply for
ideal solution and infinite dilute solution with volatile solute
precisely.
For gas is molecule (X2), K = xi2/Pi → xi = 𝐾. 𝑃𝑖 = kH 𝑃𝑖 .

This eq. is called Sieverts' law.
For real solution, activity is used for instead of concentration
at high pressure. ai = kH 𝑃𝑖 . If still using concentration or
solubility (S), empirical eq. should be used. S = a + b.P + c.P2.
where a, b, c are experimental constants. 9
Ex: Page 147

b. Ảnh hưởng của nhiệt độ đến độ tan của các khí trong chất lỏng –
Shreder equation
Investigating equilibrium of gas i and its saturated solution
with equilibrium concentration xi. i (gas) = i (liquid) + ∆Hdis
Equilibrium constant: kH = xi(sol)/xi(gas). If there is only gas
i in gas phase, xi(gas) = 1 and kH = xi(sol).
On the other hand, as Van’s Hoff equation is applied, it gives
𝜕𝑙𝑛𝐾𝑃 ∆𝐻
( ) = and ∆Hdis =λcond + ∆Hdil + ∆Hsolv . If solution is
𝜕𝑇 P 𝑅𝑇2
considered as ideal one, ∆Hdil + ∆Hsolv ≈ 0 and ∆Hdis =λcond = λi
𝜕𝑙𝑛𝐾𝑃 λ𝑖 10
→ ( ) = . This eq. is named Shreder equation.
Shreder equation
𝜕𝑙𝑛𝐾𝑃 λ𝑖
Shreder equation : ( ) =
Note:
Condensation of gas is exothermic, so λi<0 → dlnxi/dT<0 or
solubility of gas decreases with increasing temperature.
However, in case of gases dissolved in metallic liquids or
multi-metallic liquids, λdisso>0, so gas solubility will increases
with increasing temperature. This will lead to appearance of pores
in metallic solids after metallurgy. 11
Shreder equation
𝑥𝑖 𝑇
𝜕𝑙𝑛𝐾𝑃 λ𝑖 λ𝑖 𝑑𝑇
Integrating: ( ) = → 𝑑𝑙𝑛𝑥𝑖 = . 2
𝜕𝑇 P 𝑅𝑇2 𝑥𝑖 1 𝑇𝑜 𝑅 𝑇
=
where:
T° is boiling (condensing) temperature and xi = 1 means that
constituent i is pure.
T is temperature of solution and xi is mole fraction of constituent i
in saturated solution at T.
λ𝑖 1 1
→ ln xi = - ( - ) . This eq. can be used to calculate solubility
𝑅 𝑇 𝑇0 12
of gas if its boiling (condensing) temperature is known.
6.3 Sự hòa tan của chất lỏng trong chất lỏng và cân bằng dung dịch -
hơi
13
6.3 Sự hòa tan của chất lỏng trong chất lỏng và cân bằng dd - hơi
a. Hệ dung dịch lý tưởng tan lẫn vô hạn
A system of A and B are totally dissolved into each other.
Regarding Gibbs phase rule, c = k – f + 2 = 2 – 2 + 2 = 2. Hence,
2 out of 4 variables (T, P, xA and xB) are independent variables.
If T = const, c =1 → component of gas phase and P are a
function of component of liquid phase.
if P = const, c = 1 → component of gas phase and Tboil are a
function of component of liquid phase.
14
 Raoult’s law
The partial vapor
pressure of each
component of an ideal
mixture of liquids is equal
to the vapor pressure of
the pure component
multiplied by its mole
fraction in the mixture.
Pi = kR . xiL 15
 Vapor pressure - Raoult’s law
Pi = kR . xiL with kR : Raoult’s constant
If solution is composed of only one constituent, xi=1→Pi=kR.
Notes:
• Henry’s law and Raoult’s law are fit to ideal solution only and
it can be considered both of laws are the same.
• For Henry’s law, it can only apply for solute of infinite dilute
solution.
16
• For Raoult’s law, it can only apply for solvent of infinite dilute
solution.
Raoult’s area
Henry’s area
17
 P-x diagram
Applying Raoult’s
law for solution of both
constituent A and B, their P
will express as follows:
PA = PA° . xAL
PB = PB° . xBL
= PB° . (1 – xAL)
P = PA + PB
= PA°.xAL + PB° . (1-xAL) 18
= (PA° - PB°) . xAL + PB°

 Components of gaseous phase – Konovalov I law diagram
Konovalov I law is described as following eq.:
𝑥𝐵𝑉 𝑃𝐵° 𝑥𝐵𝐿 𝑥𝐵𝐿 𝑃𝐵°
= . = α . with α = is called distillation
𝑥𝐴𝑉 𝑃𝐴° 𝑥𝐴𝐿 𝑥𝐴𝐿 𝑃𝐴°
separation factor.
Notes:
• Composition of gaseous phase correlatively varies with change
of liquidus phase composition.
• The ratio of ease volatile composition to others in gaseous
19
phase is greater than its ratio in liquidus phase. This is proved
as followings:
 Composition of gaseous phase – Konovalov I law diagram
Assuming B is more volatile than A (PB° > PA° or α>1).
𝑥𝐵𝑉 𝑥𝐵𝐿
→ > and xAV +xBV = 1; xAL + xBL = 1
𝑥𝐴𝑉 𝑥𝐴𝐿
𝑥𝐵𝑉 𝑥𝐵𝐿
→ > → xBV . (1 – xBL) > xBL . (1 – xBV)
1− 𝑥𝐵𝑉 1− 𝑥𝐵𝐿
→ xBV – xBV . xBL > xBL – xBL . xBV → xBV > xBL
20
 x – x diagram
xVA + xVB = 1
and α = (xVB . xLA) / (xVA . xLB)
→ (xVB . xLA)/(α . xLB) + xVB= 1
xVB . xLA +α . xLB.xVB= α . xLB
xVB . (1 – xLB) +α . xLB.xVB= α.xLB
xVB . (1 – xLB +α . xLB) = α . xLB
xVB = α . xLB/(1 – xLB +α . xLB)
xVB = α . xLB/(1 + (α – 1).xLB)21
 T – x diagram
To express relation between T

and x, it can combine P-x equation
and Clausius-Clapeyron equation.
Vapor + Liquid
P = P°A + (P°B – P°A) . xLB
and PAorB = KAorB . exp (-λAorB/RT)
22
 Description of the diagrams
Phase diagram is an essentially useful tool to investigate

phase transition qualitatively and quantitatively. Phase transition
process can be divided into two main types:
• Constant temperature process: composition of system is varied

due to adding or removing a constituent.
• Mutable temperature process: a process that change temperature

23
of system but do not change composition of the system.
 Description of the diagrams
C=2
C=1
C=2
24
b. Hệ dung dịch thật tan lẫn vô hạn
 Vapor pressure
One of the main reasons
that makes the deviation is a
difference among interaction
forces of various molecules.
• Positive deviation: as fA-A

Điểm đẳng phí
and fB-B > fA-B → ∆H > 0,
∆U > 0, ∆V > 0 → P ↑
• Negative deviation: as fA-A and fB-B < fA-B → ∆H < 0, ∆U < 0, ∆V < 0 25
→ P↓
 Composition of gaseous phase – Konovalov II law
For the real solution, Konovalov I law cannot be applied. However,
as solutions possess small deviation and P-x diagram does not appear
azoetrope, it still can use Konovalov I law but α factor is an empirical
number not a ratio of P°B to P°A.
For P-x diagram appearing azeotropes, Konovalov stated a second

law: As solutions have P-x diagram appearing azeotropes, gaseous
phase and liquidus phase have the same composition.
26
xVB = xL B and xVA = xL A
This law can be proved as follows:
At T=const., at azeotrope P=const., thus c = k – f = 2 – 2 = 0. It

means that composition of both phases will not change during
vaporization or condensation. This kind of solution is called azeotropic
solution.
Examples for positive and negative azeotropic solutions with P-x

and T-x diagrams
27
28
29
 Phase diagram
30
c. Sự chưng cất dung dịch
 Distillation of ideal solution
 The greater α is, the easier

distillation
31
 Distillation of ideal solution
32
 Distillation of azeotropic solution
33
 Distillation of azeotropic solution
34
d. Hai chất lỏng hoàn toàn không tan lẫn
 Properties of system
Pressure of system: P = PA + PB = P°A + P°B = f(T)
Comments:
 Composition of gaseous phase depends on T, but not on composition
of liquidus phase.
 Boiling temperature does not depend on the liquidus phase
composition, it depends on ambient pressure and is smaller than
boiling temperature of each constituent in the system.
 Tboil of system keeps unchanged during boiling until one constituent
35
totally moves to gaseous phase, then the Tboil will increase to boiling
temperature of the other constituent.
 Properties of system
It can be proved by using c, with 2 constituents and 3 phases.
c = k – f + 2 = 2 – 3 + 2 = 1. It means that among three
variables (T, P and x), only one variable is independent. In other words,
at a certain T, P and x are determined.
36
 Water vapor distillation
37
 Water vapor distillation
Some organic compounds are degraded at temperature that is lower
than their boiling temperature.
• Low pressure distillation
• Water vapor distillation
As using water vapor distillation, a minimum amount of water
needed to distill 1 kg A constituent is calculated as following:
xH2O/xA = nH2O/nA = (mH2O/18)/(1/MA) and xH2O/xA = P°H2O/P°A
→ mH2O = 18.P°H2O/MA.P°A 38
e. Hai chất lỏng tan lẫn có giới hạn
 Partial dissolution of two liquids
39
 Partially miscible liquids
Regarding Gibbs phase rule, c = k – f +1 = 2 – 2 + 1 = 1 (since P=

const.)
→ At a certain T composition of two phases are determined; as T 40
varies, composition of such two phases also changes correlatively.
One-phase region
𝑛α 𝑙β
=
𝑛β 𝑙α
→ At a certain T composition of
two phases are determined; as T varies,
composition of such two phases also
changes correlatively. Two-phase region
41
At the critical point, composition

of two liquids are the same.
Below the critical point, the
system becomes one phase system
(totally miscible liquid).
Above the critical point, the
system is belong to a two-phase region.
42
 Method of plotting T-x diagram
 Chemical method:
 Physicochemical method:
43
 Kinds of phase diagram of partially miscible liquid
44
e. Ba chất lỏng tan lẫn có giới hạn
 x – x – x diagram
45
46
47
f. Quá trình chiết tách, trích ly và định luật phân bố
48
f. Quá trình chiết tách, trích ly và định luật phân bố
At T = const. and P = const., a ratio of solute concentration in

a solvent to solute concentration in another solvent is a constant
and it is called extraction distribution coefficient and independent
on the amount of solvent or solute.
K = CY/A/CY/B
49
Homework: 1, 2.
50

Chemical Thermodynamic-7-2017

Uploaded by

Copyright:

Available Formats

Chemical Thermodynamic-7-2017

Uploaded by

Document Information

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Chemical Thermodynamic-7-2017

Uploaded by

Copyright:

Available Formats

HÓA LÝ 1:

NHIỆT ĐỘNG HÓA HỌC

CBGD: Lương Huỳnh Vủ Thanh

The right side of eq. depends on T only and it signed as lnkH.

For gas is molecule (X2), K = xi2/Pi → xi = 𝐾. 𝑃𝑖 = kH 𝑃𝑖 .

Ex: Page 147

= PA°.xAL + PB° . (1-xAL) 18

= (PA° - PB°) . xAL + PB°

To express relation between T

P = P°A + (P°B – P°A) . xLB

and PAorB = KAorB . exp (-λAorB/RT)

Phase diagram is an essentially useful tool to investigate

• Constant temperature process: composition of system is varied

• Mutable temperature process: a process that change temperature

• Positive deviation: as fA-A

For P-x diagram appearing azeotropes, Konovalov stated a second

At T=const., at azeotrope P=const., thus c = k – f = 2 – 2 = 0. It

Examples for positive and negative azeotropic solutions with P-x

 The greater α is, the easier

Regarding Gibbs phase rule, c = k – f +1 = 2 – 2 + 1 = 1 (since P=

At the critical point, composition

At T = const. and P = const., a ratio of solute concentration in

You might also like