Motion: Theory

THERMOCHEMISTRY Page # 3
THERMOCHEMISTRY
Thermochemistry is the branch of physical chemistry which deals with the thermal or heat changes
caused by chemical reactions.
SPECIFIC HEAT (S)
Amount of energy required to raise the temp by 1º C of 1 gm of a substance.
Unit  Energy/gmºC
HEAT CAPACITY
The amount of heat required to raise the temperature by 1ºC or 1K of a given amount of a substance.
C=m×s
Unit  Energy/ºC
Total heat given to increase the temperature by t.
q = mst
MOLAR HEAT CAPACITY
The amount of heat required to raise the temp by 1º of 1 mole of a substance.
CLASSIFICATION OF MOLAR HEAT CAPACITY

(A) Molar heat capacity at constant pressure (Cp)
(B) Molar heat capacity at constant volume (Cv)
Relation between Cp and Cv
Cp – Cv = R (Mayor's formula)
Cp
= (Poison' Ratio)
Cv
RULES FOR THERMOCHEMICAL EQUATION
(1) It is necessary to mention physical state of all reactants and products.
(2) A  B
H = HB – HA
if H > 0 (Endothermic reaction)
H < 0  (Exothermic reaction)
If A  B + x kJ/mole
 H = –x kJ/mole
If A + x kJ/mole  B
or A B – x kJ/mole
 H = x kJ/mole
(3) After reversing a thermochemical eqn then sign of enthalpy also get changed.
e.g. A(g) + B(g)  C(g) + D(g)
H = x kJ
C(g) + D(g)  A(g) + B(g)
H = – x kJ
(4) When two reactions are added their enthalpies are also get added with their sigh.
e.g.
A(g) + B(g)  C(g) + D(g) H = x1 kJ
C(g) + E(g)  F(g) H = – x2 kJ
________________________________________
A(g) + B(g) + E(g)  D(g) + F(g)
H = x1– x2
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Page # 4 THERMOCHEMISTRY
(5) If a thermochemical equation is multiplied by a number then enthalpy is multiplied by the same
number.
e.g.
A(g) + B(g)  C(g) + D(g) H = x1 kJ
2A(g) + 2B(g)  2C(g) + 2D(g) H = 2x1 kJ
INTENSIVE PROPERTY
The property which does not depend upon the mass of substance is called intensive property.
e.g. density, refractive index, specific heat, etc.
EXTENSIVE PROPERTY
Mass dependent properties are called extensive properties

e.g.
H, S, G
* Two extensive property can be added or additive.

* Ratio of two extensive properties is Intensive.
* Intensive properties can not be added directly.
e.g. We can not add the density of two liquids to get the density of the final mixture of the two.
m
d
v
 m  dv
 dmix x(h1 + h2)A = d1h1A + d2h2A
d1h1A  d2h 2 A d1h1  d2h 2

 dmix = h1  h2 A  dmix = h1  h2
ENTHALPY
H = U + PV

Internal energy
H = U + PV + VP
(i) t constant Pressure
VP = 0 (as P = 0)
H = U + PV
(ii) At Constant Volume:
PV = 0 as V = 0
H = U + VP
(iii) If both are changing:-
H = U + (P2V2 – P1V1)
* Enthalpy is function of temperature i.e. changes with change in temperature.
H = U + PV
= U + nRT
* Enthalpy is always defined at constant temperature and it varies with variation in temperature.
H = U + PV
= nCVT + nRT = nT(CV + R)
H = n CpT
 Enthalpy at cons tan t pressure.
H = E + nRT
Enthalpy at  Enthalpy at

a constant a constant
pressure Volume
n = no. of moles of gaseous product - no. of moles of gaseous reactant.
Note:-
In chemistry, At constant temp U  0
1 mole O2 (initially)
U = nCV T
As
After reaction  n changes

 n  0
 U  0
Also as after the reaction the nature of substance formed changes which may have different value of
internal energy at the same temp.
KIRCHOFF'S EQUATION
This gives the relation between enthalpy and temperature.

* Physical state is changed at constant temperature.
Molar heat capacity at

constant pressure of A (T2)
A
–T 1)
Cp(T 2 H2
A B (T2)
(T1)
1 )
H1 Cp (T 2–T 1
B Molar heat capacity of B
(T1)
According to Hess'Law
H2 + Cp(T2–T1) = H1 +Cp1 (T2– T1)
H2 – H1 = (Cp1 – Cp) (T2– T1)
= Cp (T2– T1)
H2  H1
Cp = T T
2 1
Where
Cp = Molar heat capacity of product –– Molar heat capacity of reactant
e.g.
N2(g) + 3H2(g)  2NH3(g)
Cp = 2Cp(NH3) – Cp(N2) – 3Cp(H2)
* If the above formula (Kirchoff's eqn) is to be written for molar heat capacity at constant volume then
U2  U1
C V 
T2  T1
* If Cp is function of temperature
Cp = T2 + T
T2
Then T Cp dT  H2  H1
1
HEAT OF FORMATION
Enthalpy change during the formation of 1 mole of a compound form its most stable common occurring
form (also called reference states) of elements is called heat of formation.
C(s) + O2(g)  CO2(g)
H = Hf(CO2)
CO(g) + 1/2O2(g)  CO2(g)
H  HfCO2(g)
(because CO2 has not been formed form its element in their most stable form)
Similarly
CH2–CHO + H2  C2H5OH
H  Hf(C2H5OH)
Heat of reaction
Element Most stable form
H H2(gas)
O O2(gas)
N N2(gas)
F F2(gas)
Cl Cl2(gas)
Br Br2(gas)
I I2(solid)
C C(grapnite)
P P(white)
S S(rhombic)
* All metal exist in solid form (reference states)
ENTHALPY AT STANDARD STATE :-(Hº)

T = 25ºC = 298 K
P = 1 atm
Conc = 1M
Hº = Heat of formation at standard state
If A(g) + B(g)  C(g) + D(g) is any reaction, Heat of reaction for any thermochemical equation can be
written as
Hº = Hfº(product) – Hfº(Reactant)
If we use the above concept for the above given reaction then
Hº = Hfº(c) + Hfº(D) –Hfº(A) + Hfº(B)
Assumption :–
The heat of formation of most stable form of an element is taken as zero.
C(graphite) + O2(g) CO2(g)
Hº = Hfº(CO2) – HfºC(s) –Hfº(O2)(g)
 Hº = Hfº(CO2) (As HfºC(s) = 0 and HfºO2(g) = 0)
Another example can be taken as

H2(g) + 1/2O2(g)  H2O(l)
Hº = Hfº(H2O) – Hfº(H2) – 1/2Hfº(O2)
O O
Hº = Hfº(H2O)
* Heat of formation is always –ve as the process is exothermic.
Ex.1 From the following data,

C(s, graphite) + O2(g)  CO2(g) Hº = –393.5 kJ/mole
H2(g) + 1/2O2(g) H2O(l) Hº = –286 kJ/mole
2C2H6(g) + 7O2(g) 4CO2(g) + 6H2O(l) Hº = –3120 kJ/mole
Calculate the standard enthalpy of formation of
C2H6(g) (in kJ/mole)
Sol. From eqn(1) Hfº(CO2) = –393.5 kJ/mole
From eqn(2) Hfº(H2O) = –286 kJ/mole
From eqn (3) rHº 4 Hfº(CO2) + 6Hfº(H2O) –2 ×Hfº(C2H6) – 7×HfºO2(g)
– 3120 = 4 ×(–393.5) + 6×(–286) – 2×Hfº(C2H6) (As Hfº O2(g) = 0 )
 –3120 = –1574 –1716 – 2 ×Hfº(C2H6)
 –3120 + 3290 = – 2 ×Hfº(C2H6)
 170 = – 2 ×Hfº(C2H6)
 Hfº = – 85 kJ/mole
HEAT OF COMBUSTION
It is the enthalpy change (always –ve) when One mole of the substance undergo complete combustion.
C(s) + O2  CO2(g)
Hº = HCºC(s) = Hfº(CO2) – HfºC(s) – Hfº(O2)
Hº = = HCºC(s) = Hfº(CO2)
Other example
O O
H2 + 1/2 O2  H2O(g)
Hº = HCº (H2) = Hfº (H2O) – Hfº(H2) – 1/2Hfº (O2)

Hº = Hfº (H2) = Hfº (H2O)
Note :–
Heat of combustion is always exothermic except N2 and F2.
* N2 + O2  2NO
(It is an endothermic reaction)
* O2 + F2  OF2
(Since O has normally tendency to accept electron and opposite is happening above hence reaction
is is considered endothermic)
* Heat of reaction for any thermochemical equation can be written as (in form of heat of combustion)
Hrº = Heat of combustion of reactant – Heat of combustion of reactant .
Hrº = HCº (Reactant) – HCº (Product)
Ex.2 The enthalpy change for the reaction
C3H8(g) + H2(g)  C2H6(g) + CH4(g) at 25ºC is – 55.7 kJ/mole calculate the enthalpy of
combustion of C2H6(g). The enthalpy of combustion of H2, and CH4 are – 285.8 and – 890.0 kJ/
mole respectively. Enthalpy of combustion of propane is –2220 KJmol–1.
Sol. As we know any thermochemical eqn can be written in terms of heat of combustion as follows
Hrº = Hcº (Reactant) – HCº (Product)
Hrº = Hcº (C3H8) + HCº (H2) – {Hcº(C2H6) + HCº(CH4) }

– 55.7 = (–2220 – 285.8) – {–890 +Hcº(C2H6) }
 Hcº(C2H6) (g) = – 1560.1 kJmol–1
Problems Based on Both HOC and HOF :

Ex.3 At 300K, the standard enthalpies of formation of C6H5COOH(s), CO2(g) and H2O(l) are –408, –
393 and –286 kJmol–1 respectively. Calculate the enthalpy of combustion of benzoic acid at
(i) constant pressure
(ii) constant volume.
Sol. 7C(s) + 3H2(g) + O2(g)  C6H5COOH(s) Hº = –408 kJ
 Hfº(C6H5COOH) = – 408 kJ
C(s) + O2(g)  CO2(g) Hº = –393 kJ
 Hfº(CO2) = –393 kJ
H2(g) + 1/2O2(g)  H2O(l) Hº = –286 kJ
 Hfº(H2O) = –286 kJ
C6H5COOH(s) + 15/2O2(g)  7CO2(g) + 3H2O(l)
HCº(C6H5COOH) = 7 HfºCO2 + 3Hfº(H2O) – 4Hfº(C6H5COOH)
= 7 ×(–393) + 3× (–286) + 408
HCº(C6H5COOH) = – 3609 + 408
= –3201 kJ/mol
enthalpy of combustion at constant pressure = – 3201 kJ mol–1
Also
H = U + ngRT
–3201 = U + (–0.5) × 8.31 × 10–3 × 300
(As n = 0.5, R = 8.314 × 10–3 kJ)
 U = – 3201 + 1.2471
U = –3199.7529
 enthalpy of combustion at constant volume = – 3199.7529
BOND ENERGY
It is defined for gaseous molecules. "The enthalpy change during the breaking of one mole of bond into
isolated gaseous atoms is called bond energy of the compound"
e.g. H2(g)  2H(g)
Hº = H  H
* ge fdlh Hkh reaction dks Heat of formation of product – Heat of formation of Reactant ds form esa fy[k ldrs gsa
vkSj vxj mij okys eqn dks Hkh oSls gh fy[kk tk;s rks
Hº =  H  H = 2H ºH(g) – H º(H )
f f 2
  H  H = 2H ºH(g)
f
 Hfº H(g) =
H  H
2
Similarly
HfºO(g) =
O  O
2
 NN
HfºN(g) =
2
* Let us consider the similar bond breaking In CH4
CH4(g)  C(g) + 4 H(g)
H = 4  C  H =H ºC(g) + 4H ºH(g) – H º(CH )

f f f 4
** Enthalpy of reaction in terms of bond energy for a thermochemical eqn can be written as
Hfº = B.E.(Reactant) – B.E. (products)
Ex.4 Using the bond enthalpy data given below, calculate the enthalpy change for the reaction
C2H4 (g) + H2(g)  C2H6(g)
Data :
Bond C–C C=C C–H H–H
Bond Enthalpy 336.81 606.68 410.87 431.79
(kJ/mol) (kJ/mol) (kJ/mol)
Sol. rHº =  reac tant   product

H º =  C  C  4 C  H   H  H   C  C  6 C  H
r
Hrº = 606.68 + 4×410.87 + 431.79 –336.81 –6×410.87

= 2681.95 –2802.03
Hrº = –120.08 kJ/mol
HEAT OF HYDROGENATION
"Enthalpy change during the addition of 1 mole of H2 to an unsaturated compound. is called heat of
hydrogentation."
Hydrogenation is an exothermic process. of therefore heat of hytdrogentaiton is always –ve.
e.g.
CH2 = CH2 + H2  CH3 –CH3
Hrº = Hº (Hydrogenation) (CH2 = CH2)
+ H2
 Hrº = Hº (Hydrogenation)

of cyclohexene
Ex.5 Compare the heat of hydrogenation of the following alkene

(1) C – C – C = C (2) C – C = C – C (cis) (3) C – C = C – C (trans)
(4) C – C = C (5) C = C – C = C
C
1
Sol. Stability of alkene 
Heat of hydrogenation
The above concept is true as long as no. of double bonds are equal as heat of hydrogenation is
defined for per mole of double bond. It will be certainly larger for higher number of double bonds
irrespective of their stability.
(1) C – C – C = C (2 × H)
(2) C – C = C – C ( 6 × H)
(cis)
(3) C – C = C – C (6 × H)
(trans)
C
(4) C=C (6 × H)
C
(5) C = C – C = C (2 double bonds)
As we know trans > cis (stability)
 Heat of hydrogen (trans) < Heat of hydrogenation (cis)
H
CH3 – CH = CH – CH3 CH3– CH –CH = CH2
(less stable) ( + I of CH3 reduce the stability)
CH3 H CH2 H
C=C C–C
CH3 H CH3 H
(more stable) (more stable as nothing is

trying to reduce its stability)
of therefore decreasing order of heat of hydrogenation of alkene

5>1>2>3>4>
Ex.6 Find Hf of HCl(g) if bond energies of H2, Cl2 and HCl are 104, 58, 103 kcal/mole respectively.
Sol. H – Cl  H(g) + Cl(g)
 H  Cl = H ºH(g) + H ºCl(g) – H ºHCl(g)

f f f
1 1
103 =
2  H  H + 2  Cl  Cl – H ºHCl(g)
f
1 1
103 = ×104 + ×58 – Hfº HCl(g)
2 2
HfºHCl(g) = – 22 kcal/mol.
HEAT OF ATOMISATION
" When one mole of any substance is converted into gaseous atoms enthalpy change during the
process is called heat of atomisation." It is always + ve due to endothermic nature of the process.
HEAT OF SUBLIMATION
Enthalpy change during the conversion of one mole of solid to 1 mole of gaseous phase directly
without undergoing into liquid phase is called enthalpy of sublimation or heat of sublimation,
It is always + ve due to endothermic nature of the process.
e.g.
C(s)  C(g)
Hº = HsubºC(s) = Hfº C(g) – Hfº C(s)
O
HsubºC(s) = Hfº C(g)
HsubºC(s) = Hfº C(g) =HºatmosationC(g)
Ex.7 Using the given data, calculate enthalpy of formation of acetone(g) [All values in kJmol–1]
bond enthalpy of C–H = 413.4, C – C = 347.0 (C = O) = 728.0

( O = O ) = 495.0 , H – H = 435.8 subH of C = 718.4
O
Sol. CH3 – C – CH3 3C(g) + 6H(g) + O(g)
O
6  C  H +  C  O + 2  C  C = 3H ºC(g) + 6H ºH(g) + H ºO(g) –
f f f
Hfº( CH3 – C – CH3 )
O
6 1
6 × 413.4 + 728 + 2 × 347 = 3 × 718.4 + × 435.8 + ×495.0 – Hfº( CH3 – C – CH3 )
2 2
O
Hfº( CH3 – C – CH3 ) = – 192.3 kJmol-1
Ex.8 The enthalpy of combustion of acetylene is 312 kcal. If enthalpy of formation of CO2 and H2O
are –94.38 and –68.38 kcal respectively
Calculate C  C bond enthalpy.
Given that enthalpy of atomisation of 150 kcal and H – H bond enthalpy and C – H bond
enthalpy are 103 kcal and 93.64 kcal respectively.
5
Sol. HC  CH + O  2CO2 + H2O
2 2
HCº(CH  CH) = 2Hfº(CO2) + Hfº(H2O) – Hfº(C2H2)
– 312 = 2 × (–94.38) + (–68.38) – Hfº(C2H2)
Hfº(C2H2) = 54.86
CH  CH  2C(g) + 2H(g)
 C  C + 2  C  H = 2H ºC(g) + 2H ºH(g) – H º(CH  CH)

f f f
1
C  C +2 × 93.64 = 2 × 150 + 2 ×
2
× 103 –54.86   C  C = 160.86 kJmol –1
RESONANCE ENERGY
"The energy difference between resonance hybrid and most stable canonical structure is called
resonance energy".
Resonance energy is always –ve as nature of the process is exothermic.
Ex.9 The enthalpy of formation of ethane, ethylene and benzene from the gaseous atoms are –
2839.2,
–2275.2 and –5506 kJmol–1 respectively. Calculate the resonance energy of benzene. The
bond enthalpy of C – H bond is given as equal to + 410.87 kJ/mol.
Sol. 2C(g) + 6H(g)  C2H6 Hº = –2839.2
C2H6  2C(g) + 6H(g) Hº = 2839.2
C – C + 6C – H = 2839.2 Hº = 2839.2
C – C + 6 × 410.87 = 2839.2
C – C = 373.98 ... (1)
2C(g) + 4H(g)  C2H4(g) Hº = –2275.2
C2H4  2C(g) + 4H(g) Hº = 2275.2
C = C + 4C – H = 2275.2
C = C) = 631.72 ...(2)
6C(g) + 6H(g)  C6H6 Hº = –5506

C6H6  6C(g) + 6H(g) Hº = 5506
 3C = C + 3C – C + 6C – H + x = 5506
Putting all the values from eqn , 1, & ( 2) we get x = 23.68
 Resonance energy of benzene = – 23.68 kJ/mole
BOMB CALORIMETER
O2 gas
w
mole w m gm of
M water
Heat evolved = mst + Ct


Heat capacity of container
ms t  Ct 
Heat of combustion = – w
 
M
M
=– ms t  Ct  = – M  tms  C = – M  t [C' + C]
w w w
Heat capacity Heat capacity

of water of container
M
 H = –  t  C  Heat capacity of system
w
Ex.10 When 1.0 gm of fructose C6H12O6 (s) is burnt in oxygen in a bomb calorimeter, the
temperature of the calorimeter water increases by 1.56ºC. If the heat capacity of the
calorimeter and its contents is
10.0 kJ/ºC. Calculate the enthalpy of combustion of fructose at 298 K.
Sol. Heat capacity of the system

M
HC = C  t 
w
180
= 10  1.56 = –2808 kJ/mole
1
HEAT OF SOLUTION
Enthalpy change during the dissolution of 1 mole of salt in excess of solvent.
KCl(s) + aq  KCl (aq)
Hº = Heat of soln of KCl (s)
Note :-
(1) Heat of solution is always exothermic for the anhydrous form of salts which can form their hydrates.
e.g. CuSO4, Na2SO4, FeSO4, ZnSO4, CaCl2, LiCl etc.
CuSO4(s) + aq  CuSO4(aq) H < 0
(2) Heat of solution is endothermic for the hdyrated form of the salt.
CuSO4 . 5H2O + aq  CuSO4(aq) H > 0
(3) Heat of soln is endothermic for the salts which do not form their hydrates.
e.g. NaCl, NaNO3, KCl etc.
INTEGRAL HEAT OF SOLUTION

Enthalpy change when 1 mole of salt is dissolved in given amount of solvent.
e.g. KCl(s) + 20 H2O  KCl (20H2O) _____________(1) H2 = x
KCl(s) + 100 H2O  KCl (100H2O) _____________(2) H2 = y
HEAT OF DILUTION
Reversing the eqn (1) and adding in (2)
KCl(20H2O) + 80H2O  KCl(100H2O)
H = y – x
enthalpy change when the conc. of salt changes from one to another on the basis of dilution
 H = y – x = Heat of dilution
HEAT OF HYDRATION
Ethalpy change during the formation of hdyrated form of salt from its anhydrous form. It is always
exothermic.
CuSO4(s) + 5H2O  CuSO4.5H2O
H = Heat of hydration of CuSO4(s)
Ex.11 Heat of soln of CuSO4(s) and CuSO4.5H2O is 15.9 and 19.3 kJ/mol respectively. Find the heat
of hydration of CuSO4(s)
Sol. CuSO4(s) + aq  CuSO4(aq) ___________(1)
H = –15.9
CuSO4.5H2O + aq  CuSO4(aq) ___________(2)
H = 19.3
Reversing eqn (1) and adding (2)
CuSO4(s) + aq  CuSO4(aq)
H = 15.9
CuSO4.5H2O + aq  CuSO4(aq)
H = 19.3
______________________________________________
CuSO4.5H2O  CuSO4(s)
H = 35.2
 CuSO4(s)  CuSO4.5H2O
H = –35.2
 Heat of hydration of CuSO4(s) = –35.2 kJ/mol
HEAT OF NEUTRALISATION
Enthalpy change during neutralisation of 1 gm equivelant of Acid with 1 gm equivelant of base in
dilute soln is called heat of neutralisation.

HCl(aq) + NaoH(aq)  NaCl + H2O
H+ + Cl– + Na+ + OH–  Na+ + Cl– + H2O
H+(aq) + OH–(aq)  H2O(aq)
Hº = –13.7 Kcal
H2SO4(aq) + 2NaOH(aq) Na2SO4 + 2H2O
2H+ + SO42– + 2Na+ + 2OH–  2Na+ + SO42– + 2H2O
2H+ + 2OH–  2H2O
H = –13.7 × 2
Note :-
In case of weak Acid or weak bases the observed value is little lower because of a part of it is used
in dissociating weak Acid or weak base which is not at all completely ionised at dilute solution
unditions.
These are however, completely ionised at infinite dilution. e.g.
CH3COOH + NaOH  CH3COONa + H2O
H = –13.7 + x
As we know, H+ + OH–  H2O H = –13.7 kcal ____(1)
– +
CH3COOH  CH3COO + H Hº = x ____(2)
Add eqn (1) + (2)
__________________________________
CH3COOH  OH–  CH3COO– + H2O Hº = y
Ex.12 100 ml 0.5M H2SO4(strong Acid) is neutralised by 200 ml 0.2 M NH4OH. In a constant pressure
calorimeter which results in temperature rise of 1.4ºC. If heat capacity of calorimeter
constant is
1.5 kJ/ºC.
Which statement is/are correct.
Given: HCl + NaOH NaCl + H2O + 57 kJ
CH3COOH + NH4OH  CH3COONH4 + H2O + 48.1 kJ
(A) Ethalpy of neutralisation of HCl v/s NH4OH is –52.5 kJ/mol
(B) Ethalpy of dissociation (ionisation) of NH4OH is 4.5 kJ/mol
(C) Ethalpy of dissociation of CH3COOH is 4.6 kJ/mol
(D) H for 2H2O(l)  2H+(aq) + 2OH–(aq) is 114 kJ
Sol. (A) Total heat evolved due to the neutralization = C × t = 1.5 × 1.4 = 2.1
M. eq of H2SO4 = 100 ×0.5 = 50
M.eq of NH4OH = 20 × 0.2 = 40
Since NH4OH is limiting hence energy will evolved according to it.
 0.04 gm eq produces 2.1 kJ
2 .1 210
1 gm eq produces = 1 = = 52.5
0.04 4
 Heat of neutralisation = –52.5 kJ
(B) –57 + x = – 52.5
 x = – 52.5 + 57 = 4.5
 Enthalpy of dissociation of NH4OH = 4.5 kJ/mol
(C) 57–(x + y) = 48.1

 x + y = 8.9
 4.5 + y = 8.9  y = 4.4

 enthalpy of dissociation of CH3COOH = 4.4 kJ/mol
(D) As we know
H+ + OH–  H2O H = –57
+ –
 2H + 2OH  2H2O H = –57× 2
 2H2O  2H+ + 2OH– H = 114 kJ
 Option A, B, and D are correct.
BORN HABER CYCLE

Ionisation Energy :-
The minimum amount of energy required to remove one electron form the outermost shell of an
isolated gaseous atom is called ionisation energy of the element.
Electron affinity:-
Amount of energy released when an extra electron is added to an isolated gaseous atom.
Lattice Energy :
Amount of energy released when 1 mole of gaseous cation and 1 mole gaseous anion combine to
each other and form 1 mole of ionic compound is called lattice energy.
Na+(g) + Cl–(g)  NaCl(s) + heat

Lattice energy
q1q 2
Hlattice  2
r 
 r 
Ex.13 The born-Haber cycle for formation of rubidium chloride ((RbCl) is given bellow (the
enthalpies are in kcal mol–1)
1 105
Rb(s)  Cl2 (g)   RbCl(b)
2
+20.5 –159.5
28.5
+
Rb (g)
Rb(g)
Cl(g)  Cl(g)
X
96.0
find the value of X?

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THERMOCHEMISTRY Page # 3

CLASSIFICATION OF MOLAR HEAT CAPACITY

Mass dependent properties are called extensive properties

* Two extensive property can be added or additive.

 dmix x(h1 + h2)A = d1h1A + d2h2A

d1h1A  d2h 2 A d1h1  d2h 2

 Enthalpy at cons tan t pressure.

Enthalpy at  Enthalpy at

After reaction  n changes

This gives the relation between enthalpy and temperature.

Molar heat capacity at

ENTHALPY AT STANDARD STATE :-(Hº)

Another example can be taken as

Ex.1 From the following data,

Hº = HCº (H2) = Hfº (H2O) – Hfº(H2) – 1/2Hfº (O2)

Hrº = Hcº (C3H8) + HCº (H2) – {Hcº(C2H6) + HCº(CH4) }

Problems Based on Both HOC and HOF :

CH4(g)  C(g) + 4 H(g)

H = 4  C  H =H ºC(g) + 4H ºH(g) – H º(CH )

Sol. rHº =  reac tant   product

Hrº = 606.68 + 4×410.87 + 431.79 –336.81 –6×410.87

 Hrº = Hº (Hydrogenation)

Ex.5 Compare the heat of hydrogenation of the following alkene

(more stable) (more stable as nothing is

of therefore decreasing order of heat of hydrogenation of alkene

 H  Cl = H ºH(g) + H ºCl(g) – H ºHCl(g)

bond enthalpy of C–H = 413.4, C – C = 347.0 (C = O) = 728.0

 C  C + 2  C  H = 2H ºC(g) + 2H ºH(g) – H º(CH  CH)

6C(g) + 6H(g)  C6H6 Hº = –5506

Heat evolved = mst + Ct

Heat capacity Heat capacity

INTEGRAL HEAT OF SOLUTION

dilute soln is called heat of neutralisation.

(C) 57–(x + y) = 48.1

 4.5 + y = 8.9  y = 4.4

BORN HABER CYCLE

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