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Capitolul2 Chimie
Capitolul2 Chimie
2. THERMODYNAMICS OF
CHEMICAL PROCESSES
Main Objectives
• the thermal effects of chemical transformation;
• the quantity of work, accompanying thermodynamic
process which can include a chemical reaction;
• the laws describing the processes in which the energy
pass from one state to another;
• the possibility, the direction and the limits of natural and
industrial process;
• the organization or disorganization state of
thermodynamic systems;
• the chemical system and thermal equilibrium after
physical – chemical transformations;
• establish the determining conditions for equilibrium.
System
• t ® °C (Celsius degrees)
• T ® K (Kelvin degrees) (T = t + 273,16)
• °F = 9/5 °C + 32 (Fahrenheit degrees)
(anglosaxon system)
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Sign convention
(+) any quantity which increases the energy of the system;
(-) any energy lost by the system.
Examples:
– Heat:
(+) received by the system (evaporation, endothermic
reaction)
(-) lost by the system (solidification, exothermic reaction)
– Work:
(+) performed by the surrounding on the system
(compression)
(-) performed by the system (expansion)
Prof. Ileana Rau
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Exemples :
• Reversible Processes (perfect gaz):
– Isotherm process (constant temperature)
– Isochoric process (constant volume)
– Adiabatic process
– Isobar process (constant pressure):
A new state function is introduced in order to characterize
the isobar process: H – Enthalpy, calorific function of Gibbs
The thermal effects of all process which take place at
constant pressure (chemical reactions, phase transitions,
solubilization) represent the change in enthalpy for that
system
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Q m
C= n=
nDT M
• Cv – the molar heat capacity at constant volume - the change of the molar internal
energy of the substance with the temperature, at constant volume
• Cp – the molar heat capacity at constant pressure - the change of the molar
enthalpy of the substance with the temperature, at constant pressure
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Cp – Cv = R - Mayer equation
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2.2.2.2 Thermochemistry
In thermodynamics and physical chemistry,
themochemistry is the study of the heat
evolved or absorbed in chemical reactions.
Thermochemistry, generally, is concerned with
the heat exchange accompanying
transformations, such as mixing, phase
transitions, chemical reactions, etc, which
include calculations of quantities such as the
heat capacity, heat of absorption, heat of
formation, etc.
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n 1 A1 +n 2 A2 +n 3 A3 + ... +n i Ai + ... ®n 1' A1' +n 2' A2' + ...n i' Ai' + .... ± Dr H
If is (+) the reaction is endothermic reactions
Dr H
and if is (–) the reaction is exothermic.
Dr H
Dr HT , P = ån i' H i' - ån i H i
prod react
N 2 + 3H 2 ® 2NH3
Exemple
Dr H T , P = 2 H NH3 - 3H H 2 - H N 2
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a) Heat of formation
Dr H T , P = ån i'Df H i' - ån i Df H i
prod react
• In tables
Df H 298
0
- standard enthalpy of formation
• The standard enthalpy of formation of a substance is
the standard reaction enthalpy for the formation of the
compound from its elements in their reference states.
• c. s. : t = 25°C si p = 1 atm.
• c. n. : t = 0°C si p = 1 atm.
• c. b. : t = 37°C si p = 1 atm.
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b) Heat of combustion
• The heat of combustion is the energy
released as heat when one mol of a
compound undergoes complete combustion
to upper stable oxides.
Exemple:
CH 4(g) + 2O 2(g) ® CO 2 (g) + 2H 2O(l) Dc H 298
0
= -212,79 kcal / mol
Dr H T , P = ån i Dc H i - ån i' Dc H i'
react Prof. Ileana Rau prod
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CO
DrH2 DrH3
½ O2 ½ O2
DrH1
C CO2
O2
Dr H1 = Dr H 2 + Dr H 3
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b) Kirchhoff’ s law
D HT2 , P = D HT1 , P + ò Dr CP dT
r r
T1
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CP = a + bT + cT 2
Dr CP = Dr a + Dr bT + Dr cT 2 + ...
Generally: T1 = 298K şi P = 1 atm. (standard heat of formation)
"!
Δ! 𝐻"#! = Δ! 𝐻$%&
#
+ % Δ! 𝑎 + Δ! 𝑏𝑇 + Δ! 𝑐𝑇2+. . . 𝑑𝑇
$%&
Dr C p > 0 T DrH
Dr C p < 0 T DrH
Dr C p = 0 T DrH - constant
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Exemple:
CH 4 (g) + 2O2 (g) ® CO 2 (g) + H 2O(l) Dr H1
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Consequence
Df H = -Dd H
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Sign convention W
(+) – for heat received by the system
(-) – for heat lost by the system
W = Q1 - (-Q 2) = Q 1+ Q 2
The efficiency is given by: W Q1 + Q2
h= =
Q1 Q1
Sadi Carnot (1824) established the ideal efficiency of heat
engines for an engine which work through cycles formed
from two isotherm transformations (constant temperature)
and two adiabatic transformations (Q = ct). Such a cycle is
called Carnot cycle. T -T
h= 1 2
TProf.
1 Ileana Rau
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dQ £ TdS
TdS ³ dU + pdV
dQ = dU + pdV (I law) st
the correlation expression
between Ist law and IInd law of
thermpdynamics
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D ST = D ST + ò
r r
dT ± n i
1
+ò dT 2
2 1
T1 T Ttr T T
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tr
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Exemplu:
Calculate the reaction entropy:
Al2O3 + 3C ® 2Al + 3CO
at 1000 K and 1 atm.
It is known: Dr S 0 298 = 138,88 cal / K , aluminium melting
temperature 930 K, Δ!"#$ 𝐻%#& = 2500 𝑐𝑎𝑙/𝑚𝑜𝑙
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b) Thermodynamic potentials
Helmholtz Free Energy (A or F),
Gibbs Free Energy (G)
The Helmholtz free energy is a
U - TS º A thermodynamic potential which measures
the “useful” work obtainable from a closed
thermodynamic system at a constant
temperature.
In a system, at constant temperature and
pressure can take place spontaneously
G º H - TS only the processes in which the Gibbs free
energy is decreasing (dG )T , P < 0
At equilibrium the Gibbs free energy
of the system is minimum and it is
maintained constant (DG )T , P = 0
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æ ¶Dr G ö
D G = D H + T çç
r r
÷÷
è ¶T ø P
Gibbs – Helmholtz equation establishes the
connection between the chemical affinity, Dr G
and the reaction heat Dr H
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• Planck affirmation:
DS
At 0 K not only is zero but also the molar entropy (S) of any
crystalline pure element is zero.
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æ ¶G ö æ ¶G ö æ ¶G ö
dG = - SdT + VdP + çç ÷÷ dn1 + çç ÷÷ dn2 + çç ÷
÷ dni + ...
è ¶n1 øT , P , n 2 , n3 ,..., ni è ¶n2 øT , P.n , n ,.., n
1 3
è ¶ni øT , P , n
i j ( j ¹i )
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v1 A1 + v2 A2 + ... + vi Ai + ... v'1 A'1 + v'2 A'2 + ... + v'i A'i + ...
µ1 µ2 µi µ’1 µ ’2 µ ’i
(D G )
r
T ,P = å vi' µi' - å vi µi = 0
the thermodynamical
condition of the chemical
prod react
equilibrium
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Dr GT0 = -RT ln K a
Ka – is the equilibrium constant, calculated with activities
Õa
'
' vi
i
ai is the activity of ith component at
Ka = prod
equilibrium. It is a kind of “effective”
Õa
react
vi
i mole fraction
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Õ pi'
v i'
Õp
vi
i
react
For very diluted solutions activities can be replaced by
corresponding concentrations
Ka ® K x or Ka ® Km or Ka ® Kc
ci – molar
xi – molar ratio mi – molal concentration
at equilibrium concentration (mols of
ni (moles of substance in 1L
xi = substance in 1 kg
nt of solution) at
of solvent) at equilibrium
equilibrium
Dr GT0 = -RT ln K x (Dr GT0 ) m = -RT ln K m (Dr GT0 ) c = -RT ln K c
(D G ) ¹ (D G ) ¹ (D G )
r 0
T
r 0
Prof.TIleana
m Rau
r 0
T c
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Þ Kp = × = K x P Dv
v v v 1 v
x1 x2 x3 ... xi ...
2 3å v i i
P i
Dv = å vi' - å vi
Prod React
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b) piV = ni RT
u1' u 2' u3' ui'
( RT )å
'
c1' c2' c3' ... ci' ... u i
= K c (RT )
Du
Kp = ×
u1 u 2 u3
c1 c2 c3 ... ci ... ui
(RT )åu i
Dv = 0 Þ K p = K x = Kc
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Exemple
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Dr H T0 Dr ST0
T
Dr C p
Dr ST0 = Dr S298 + ò
0
ln K a = - + dT
RT R 298 T
0 0
/ /
Δ+ 𝐻,-. Δ+ 𝑆,-. 1 1 +
Δ+ 𝐶1
ln 𝐾* = − + − - Δ 𝐶1 𝑑𝑇 − - 𝑑𝑇
𝑅𝑇 𝑅 𝑅 𝑇 𝑇
,-. ,-.
This equation solves the most important problem of chemical equilibrium:
the integral calculus of equilibrium constant from thermodynamical data -
reaction heat, molar heat capacities, and entropies
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æ Dr G 0 ö
d çç ÷÷
1 Dr G 0 d ln K a 1 è T ø
ln K a = - =-
R T dT R dT
æ Dr G 0 ö
d çç ÷÷
è T ø =-D H
r 0
Gibbs Helmholtz Equation
dT RT 2
d ln K a Dr H
= van’t Hoff equation
dT RT 2
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d ln K a Dr H
=
dT RT 2
So the increase of the
D H >0
r 0
; T Ka temperature will have as
effect the shift of the
reaction to the right side
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Dv > 0 ; P Kx
Dv < 0 ; P Kx
Dv = 0
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Exemple
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