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C3H6 (g) + 9/2 O2(g) 3CO2 (g) + 3 H2O (l) Hc


We can write reaction in stepwise manner
(1) C3H6 (g) + H2(g) C3H8 (g) H1
(2) C3H8 (g) + 5 O2(g) 3CO2 (g) + 4 H2O (l) H2

(3) H2O (l) H2 (g) + ½ O2 (g) H3


adding (1), (2), (3), we obtain

C3H6 (g) + 9/2 O2(g) 3CO2 (g) + 3 H2O (l)

the same as combustion of C3H6


According to the 1st law
Hc = H1 + H2 + H3
Example: Find standard enthalpy of reaction at 298 K for

C 6H6(l) + 15/2 O2(g) 6CO2(g) + 3H2O (l)

H rO = �
6 
� fH O
(CO2 , g ) + 3H O
f ( H 2 O , l ) �- 
� � f (C6 H 6 , l ) �
� H O

= (6mol)(-393.51 kJ/mol) + (3mol)(-285.83 kJ/mol)


– (1mol)(49kJ/mol)

= -3268 kJ
Find Standard Enthalpy of Formation
The enthalpy of combustion for H2, C(graphite) and CH4 are - 285.8,
- 393.5, and - 890.4 kJ/mol respectively. Calculate the standard
enthalpy of formation Hf for CH4. (correction made)

Solution : C (graphite) + 2 H2  CH4 Hf° = _____


Explain these from the data
2 *(-285.8)
2 H2(g) + O2(g)  2 H2O(l) H = - 571.6 kJ

C(graphite) + O2(g)  CO2(g) H = - 393.5 kJ


CO2(g) + 2H2O(l)  CH4(g) + 2O2(g) H= 890.4 kJ (+ve)
(1) + (2) + (3)

C (graphite) + 2 H2  CH4 Hf° = - 74.7 kJ


Heats of Reaction, U & H
For a reaction Reactants  Products
The change in internal energy is
U = Uproducts – UReactants
= qrxn + w
The change in internal energy U is the heat of reaction under constant
volume, qv, U = qv, because w = 0, no P-V work.
Enthalpy H is the heat of reaction under constant pressure qp, H = qp
Under this condition, work done on or by the system, is w = – P V.
reactants
Thus, U = qp - P V = H – P V
or H = U + P V H U + P V

products
Explain U and H .
Relation between H and U

• H = U + pV
 H = U + (pV) for a process (change
- (pV) is small for processes involving condensed phases (solids
and liquids) only
 (pV) is generally significant for processes involving gases
 H  U for processed involving condensed phases only
- (pV) = (nRT) for a gas (ideal gas)
 H = U + (ngasRT) for processes involving gases
Change in Temperature of Gas

 (ngasRT) = ngasR T
– for a change in temperature of a given amount of gas
 H = U + ngasR T
– relation between the change in enthalpy and internal energy of a
given amount of gas when the gas is heated or cooled
Relation between H and U for a Reaction
Involving Gases

• aA(g) + bB(g)  cC(g) + dD(g)


– reaction is assumed to take place at constant temperature
 ngas = (c + d) - (a + b)
 ngas is the change in number of moles of gas upon reaction
 (ngasRT) = RT ngas

 H = U + RT ngas
– relation between the enthalpy change and the change in internal
energy for a reaction taking place at constant temperature
• Ex. Calculate the standard reaction enthalpy for the combustion of
propene gas (CH2=CHCH3) and ∆U at 25oC if you have:

• 2CH2=CHCH3(g) +2H2(g) 2CH3CH2CH3(g) ∆HӨ = -248 kJ/mol (1)


• CH3CH2CH3(g) + 5O2(g) 3CO2(g) + 4H2O(L) ∆HӨ = -2220kJ/mol (2)
• H2O(l) H 2(g) + 0.5O2(g) ∆HӨ = 286 (3)
--------------------------------------------------------------------------------------------------------------
CH2=CHCH3(g) +9/2 O2(g) 3CO2 (g) + 3H2O (g) ∆HӨ = ------ kJ/mol
By devided eq. (1) on 2 and sum the eqs.

CH2=CHCH3(g) + H2(g) CH3CH2CH3(g) ∆HӨ = -124 kJ/mol


CH3CH2CH3(g) + 5O2(g) 3CO2(g) + 4H2O(L) ∆HӨ = -2220kJ/mol
H2O(l) H 2(g) + 0.5O2(g) ∆HӨ = 286
-----------------------------------------------------------------------------------------------------------------
CH2=CHCH3(g) +9/2 O2(g) 3CO2 (g) + 3H2O (g) ∆HӨ = ------ kJ/mol
H = U + RT ngas
ngas = (3+3)-(1+4.5) = 0.5
U = H – (0.082 *298*0.5)= -------- kJ/mol
Ex. Calculate the enthalpy of the following reaction at 298 oK
C2H6 + Cl2 C2H6Cl + HCl H0 = ------- Kcal
Given that:
C2H6 + 7/2 O2 2CO2 + 3H2O H0 = - 341 Kcal/mol
4C2H6Cl + 13 O2 2Cl2 + 8CO2 + 10H2O ∆H0 = - 1230 Kcal/mol
H2 + ½ O2 H 2O ∆H 0 = - 58 Kcal/mol
½ H2 + ½ Cl2 HCl ∆H 0 = - 2 Kcal/mol
-----------------------------------------------------------------------------------------
.By devided eq. (2) on - 4 and sum the eqs

C2H6 + 7/2 O2 2CO2 + 3H2O H0 = - 341 Kcal/mol


½ Cl2 +2CO2 +10/4 H2O C2H6Cl + 13/4 O2 ∆H0 = +1230/4 Kcal/m
H2 + ½ O2 H 2O ∆H0 = - 58 Kcal/mol
½ H2 + ½ Cl2 HCl ∆H 0 = - 2 Kcal/mol
-----------------------------------------------------------------------------------------
C2H6 + Cl2 C2H6Cl + HCl ∆H0 = ------- Kcal
Temperature dependent
from
 dH = C P dT
T2

H  T2  - H  T1  = C dT

P
T1
T2

H  T2  = H  T1  + C P dT ---------- (*)
T1

aA + bB cC + dD

H = (cHm,C + dHm,D) - (aHm,A + bHm,B)


Using (*)

 
T2
  T2

H  T2  =  c H m ,C  T1  + T Cpm,C dT  + d  H m , D  T1  + 
T Cpm,D dT 
  
  1   1 


 
T2
  T2

-  a H m , A  T1  +  Cp dT  + b H m , B  T1  + 
T m, B 
Cp dT
  m , A
 
  T1   1 

H  T2  =   cH  T  +
m ,C 1 dH m , D  T1   -  aH  T  +
m, A 1 bH m , B  T1 
T2

+  (Cp
T1
m ,C + Cpm , D - Cpm , A - Cpm , B )dT

T2

H  T2  = H  T1  +  C P dT
Kirchhoff ’s Law
T1

Cp =  i Cpm,i  prod  -  i Cpm,i  reac 


i i
Example 3.9 The standard enthalpy of gaseous water and
liquid water at 250C are -241.82 and -285.83 kJ/mol,
respectively. Find the standard heat of vaporization of water.
Given Cpm,l = 75.29 and Cpm,g = 33.58 J/Kmol

H2O(l) H2O(g) HOvap = ?


373

HOvap = HO(1000C) = HO(250C) +  Cp


298
m, g - Cpm ,l dT


= H o 25o C  + Cp m, g - Cp m,l   373 - 298


H o 25o C  = H of  H 2O, g  - H of  H 2O, l 
= - 241.82 -  - 285.83 kJ / mol
Cp m, g - Cp m ,l  =  33.58 - 75.29 = - 41.71J / Kmol
H vap
0
= 44.01 kJ / mol -  41.71x10 -3 kJ / Kmol  75K 
= 40.88 kJ / mol
Summary
• Thermodynamics tells which way a process will
go
• Internal energy of an isolated system is constant (work
and heat). We looked at expansion work (reversible
and irreversible).
• Thermochemistry usually deals with heat at constant
pressure, which is the enthalpy.

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