Professional Documents
Culture Documents
Thermo Chemistry
Thermo Chemistry
the associated energy changes. The main form of this energy is heat.
exothermic reaction.
Endothermic Reaction
Energy
Products
ΔH = +ve
Reactants
Reaction pathway
Exothermic reaction
Energy
Reactants
ΔH = -ve
Products
Reaction pathway
Definitions of some heat changes
The higher the charge density of the ion, the more exothermic the enthalpy of
positive, if the final temperature of the solution is less than the initial temperature,
while is exothermic, if the final temperature is greater than the initial temperature.
Its value is constant for a given pair of strong acid and base.
(6) Atomization Energy: It the enthalpy associated with the formation of one mole of
Its value is always positive (endothermic). Some examples are given below
bond energy is used if two or more of the same kind of bonds are broken,
illustrated below
The bond energy of C-H bond in CH4 is correctly designated as average bond
energy, since more than one of the same type of bond are broken, in succession.
(8) Electron Affinity: It is the heat change that accompanies the gain of one
The first electron affinity of an element is exothermic, while subsequent values are
(9) Lattice Energy: Is the energy released when one mole an ionic crystal is formed
from its constituent gaseous ion, under standard condition. Lattice energy is always
constituent ions.
The higher the charge densities of the ions, the more exothermic the lattice
energy.
It is an energy cycle that gives details of all the enthalpy changes associated with a
given chemical reaction. The information obtainable from the cycle can be used to
simple equation, using the knowledge of Hess’ law. The states that the heat
taken by the reaction. The law treats the enthalpy change of a reaction as a state
CO2(g) + 2H2O(l)
compounds
(ii) Use the data and the equation derivable from the Born-Haber cycle to
ΔH°f (C2H2O)
(i) 2C(s) + H2(g) + 1/2O2(g) C2H2O(l)
2ΔH°c(C) ΔHºc(H2)
ΔH°c (C2H2O)
2CO2(g) + H2O(l)
energies
ΔHºf(C2H5OH)
2C(s) + 3H2(g) + 1/2O2(g) C2H5OH(l)
The standard enthalpy changes of atomization of the elements silicon and chlorine
(ii) Use the equation derivable from the cycle to calculate the average bond energy
Solution:
(i)
ΔHºf(SiCl4)
Si(s) + 2Cl2(g) SiCl4(l)
ΔH°at(Si) 4×ΔH°at(Cl)
4×B.E.(Si-Cl)
Si(g) + 4Cl(g)
(ii) Applying Hess’ law, the equation below can be derived from the energy
cycle drawn
M+(g) + X(g)
ΔHºat(X)
M(g) + 1/2X2(g)
ΔHºat(M)
L.E.(MX)
M(s) + 1/2X2(g)
0
ΔHºf(MX)
MX(s)
By applying Hess’ law, the below equation can be obtained
L.E. (MX) = ∆Hºf (MX) – [∆Hºat (M) + ∆Hºat (X) + 1st I.E. (M) + 1st E.A. (X)]
Use the following data to construct a Born-Haber cycle and calculate the lattice
ΔH°at(S)
Ba(g) + S(s)
ΔH°at(Ba)
Ba(s) + S(s)
0
ΔH°f (BaS)
BaS(s)
The equation below can be obtained from the energy cycle drawn above
L.E. (BaS) = ∆Hºf (BaS) – [∆Hºat (Ba) + ∆Hºat (S) + 1st I.E. (Ba) + 2nd I.E. (Ba)
(a)Write the equation which represents the lattice energy of calcium fluoride
(b) (i) Construct a Born-Haber cycle which can be used to calculate the lattice
(ii) Calculate the lattice energy of calcium fluoride using the following data
Ca2+(g) + 2F(g)
ΔH°at(Ca)
Ca(s) + F2(g)
0
ΔH°f(CaF2)
CaF2(s)
(b) (ii) L.E. (CaF2) = ∆Hºf (CaF2) – [∆Hºat (Ca) + 2×∆Hºat (F) + 1st I.E. (Ca) + 2nd I.E. (Ca)
associated with chemical reactions. There are various types of energy, but
thermodynamic process
thermodynamic process.
(d) Open System: A system in which mass and energy are transferred
(g) Internal Energy (U): It is the energy associated with the internal processes
(h) Heat energy (q): This is the internal energy transferred from one substance to
the system is the same as the enthalpy, H, of the system. The portion of H that is
unavailable for work is the product of temperature, T, and the entropy, S, of the
system, TS. The remaining portion, that is available for work is called the Gibb’s Free
Energy, G.
G = H – TS 1.1
ΔG = ΔH –TΔS 1.2
Solution:
ΔSºreaction = (213.8 + 130.5) – (197.9 + 188.7) = 344.3 – 386.6 = -42.3 J K-1 mol-1
ΔGº = ΔHº - TΔSº = [-41.2 – (300 ×(-0.0423)] = -41.2 + 12.69 = -28.51 kJ mol-1
The value of ΔGº is negative, which implies the reaction is spontaneous. A positive ΔGº
a system tends to move towards a state of low energy. Equation 1.2 or 1.3 shows that
such state is encouraged by a more negative ΔH and/or a more positive ΔS. This implies
that a process, in which the system move from high energy to low energy state, tends to
proceeds spontaneously. In the same manner, a process in which the system moves from