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Chemical Energetics (English)
Chemical Energetics (English)
KEY CONCEPTS
Intensive properties
Open System
Those properties whose values, on
Exchange of matter and
Properties of system
division of system, remain same in any
energy both occurs with
part of the system are called intensive
surroundings
properties.
(Part of the universe under
study is system)
System
Ex : -
I II
Isolated System III IV
Neither matter nor energy is
This container is filled with an ideal gas at a
exchanged with surrounding definite T.
Intensive properties : Pressure, temperature,
concentration, density, refractive index,
2. Surrounding viscocity, surface tension, molar volume,
dipole moment gas constant, specific heat
capacity, vapour pressure, specific gravity,
Part of universe excluding system is surroundings.
dielectric constant, EMF of a dry cell etc.
Extensive properties : Volume, energy, heat
capacity, enthalpy, entropy, free energy, length,
mass etc.
CAREER POINT, CP Tower, Road No.1, IPIA, Kota (Raj.), Ph: 0744-3040000 CHEMICAL ENERGETICS 49
4. Process 5. Internal energy (U or E)
E = Et + Ev + Er + Ee + En + Ep etc.
Isothermal
T = 0 Absolute value of E can not be determined.
U = 0(for ideal gas)
H = 0(for ideal gas)
E can be found for a process
Isobaric
E T (for ideal gas)
P = 0
H = QP
E = nCVT (Here CV = molar heat capacity at
Isochoric constant volume)
V = 0
WP-V = 0 6. Reversible (or quasi-static) and
U = QV Irreversible process
Adiabatic
(i) If a process is carried out in such a way that at
Q=0 every moment the system departs only
infinitesimally from an equilibrium state the
Cyclic process is called a quasi-static process.
U = 0
Process
V
(cyclic process
on P-V graph)
Free expansion
Pext = 0
Q=0
WP-V = 0
U = 0
(for ideal gas)
Polytropic
PVa = constant
a = polytropic index
If a = then process is
adiabatic
P-V work in various processes
(for ideal gas) w = – PdV (P = External pressure)
Isothermal
process
7. P-V work in various processes
Isochoric
Q = n × C × T …(2) Process
m H = U + VP
(n = no. of moles = and
M
C = molar heat capacity ) Adiabatic
Process
(iii) At constant volume
H = nCPT
(iii)
U = n C v,m (T2 – T1)
Adiabatic process
rH
products
BH m (B) |
reactants
B | H m (B) (E) Hess's Law of constant heat summation
The heat absorbed or evolved in a given chemical
two cases may be distinguished. reaction is the same whether the process occurs in
(a) Exothermic reaction : In a case where the one step or several steps.
enthalpy of products is less than that of (F) Enthalpy of Combustion
reactants, we have
It is the enthalpy change when one mole of a
rH = negative
compound combines with the requisite amount of
(b) Endothermic reaction : In a case where oxygen to give products in their stable forms.
the enthalpy the of products is greater than
that of reactants, we have (G) Integral Enthalpy of solution : The integral
enthalpy of solution at the given concentration is
rH = positive the enthalpy change when one mole of the solute is
(D) Enthalpy of formation dissolved in a definite quantity of solvent to
produce a solution of a desired concentration.
(i) Definition : The standard enthalpy of
formation of the compound is the change in the While recording integral enthalpies of solution it is
standard enthalpy when one mole of the a general practice to state the amount of the solvent
compound is formed starting from the requisite in which 1 mole of solute is dissolved. Thus
amounts of elements in their stable state of
aggregation. HCl(g) + 10 H2O(l) HCl(10 H2O)
(ii) The standard enthalpy of formation of element rH1 = – 69.488 kJ mol–1
in its stable state of aggregation at one bar
pressure and at specified temperature is Similarly
assigned a zero value.
(i) HCl(g) + 25 H2O)(l) HCl(25 H2O) ;
The specified temperature is usually taken as
25ºC. rH2 = – 72.266 kJ mol–1
A few examples are : (ii) HCl(g) + 40 H2O(l) HCl(40 H2O) ;
fHº (O2, g) = 0 rH3 = – 73.023 kJ mol–1
fHº(C, graphite) = 0
(iii) HCl(g) + 200 H2O(l) HCl(200 H2O) ;
fHº(C, diamond) 0
rH4 = – 74.203 kJ mol–1
fHº(Br2, ) = 0
(iv) HCl(g) + aq HCl (aq) ; rH5 = – 75.145 kJ mol–1
fHº(S, rhombic) = 0
Where rH5 represents the limit of enthalpy change
fHº(S, monoclinic) 0 when 1 mole of hydrogen chloride gas is dissolved
in a very large quantity of water. The resultant
fHº(P , white) = 0 solution is known as an infinite diluted solution.
fHº(P, black) 0 (H) Integral Enthalpy of Dilution : The integral
enthalpy of dilution is the change in enthalpy when
(iii) Enthalpy of reaction from Enthalpies of
a solution containing 1 mole of solute is diluted
formation : from one concentration to another.
rHº = B fHº (B) (I) Differential Enthalpy of Solution : It is the
product enthalpy change when 1 mole of solute is dissolved
in a very large volume of a solution of known
concentration so that there occurs no appreciable By convention, the standard enthalpy of formation
change in concentration of the solution. of H+(aq) is taken to be zero.
(J) Differential Enthalpy of Dilution : It is enthalpy Thus, rHº (OH–, aq) = – 229.99 kJ mol–1
change when 1 mole of solvent is added to a large
(P) Bond Enthalpies
volume of the solution of known concentration so
that there occurs no appreciable change in the (i) The bond enthalpy is the average of enthalpies
concentration of the solution. required to dissociate the said bond present in
different gaseous compounds into free atoms or
(K) Enthalpy of hydration : Enthalpy of hydration of a
radicals in the gaseous state.
given anhydrous or partially hydrated salt is the
enthalpy change when it combines with the (ii) The term bond enthalpy may be distinguished
requisite amount of water to form a new hydrated from the term bond dissociation enthalpy which
stable salt. For example, the hydration of anhydrous is defined as follows.
cupric sulphate is represented by
The bond dissociation enthalpy is the enthalpy
CuSO4(s) + 5H2O(l) CuSO4.5H2O(g) required to dissociate a given bond of some
specific compounds.
(L) Enthalpy of Neutralization : Enthalpy of
neutralization is defined as the enthalpy change (Q) Enthalpy of Transition
when one mole of H+ in dilute solution combines Enthalpy of transition is the enthalpy change when
with one mole of OH– to give rise to undissociated one mole of one allotropic form changes to another.
water i.e., H+(aq) + OH–(aq) H2() For example
20. Gibbs free energy (G) and spontaneity dG = dU + PdV – TdS + VdP – SdT
dG = VdP – SdT
A new thermodynamic state function G, the Gibbs
free energy is defined as : • At constant temperature
G = H – TS G
at constant temperature and pressure dG = VdP or V
P T
G = H – T S
If (G)T, P < 0 process is irreversible • At constant pressure
(spontaneous) G
dG = – SdT or S
(G)T, P = 0 process is reversible T P
(Equilibrium)
(G)T, P > 0 process is impossible Relationship between G and Wnon-PV
(non spontaneous) dU = q + WPV + Wnon-PV
The use of Gibbs free energy has the advantage that for reversible process at constant T and P
it refers to the system only (and not surrounding)
To summaries, the spontaneity of a chemical dU + PdV – TdS = Wnon-PV
reaction is decided by two factors taken together : H – TdS = Wnon-PV
(i) the enthalpy factor and
(ii) the entropy factor (Gsystem)T,P = Wnon-PV
The equation G = H–T S takes both the factors – (Gsystem)T,P = (Wnon-PV)system
into consideration. Non-PV work done by the system = decreases in
(Hr)T.P. (Sr)T.P. (Gr)T.P. Remarks gibbs free energy
– ve + ve Always – ve Reaction is
spontaneous Some facts to be remembered :
+ ve – ve Always + ve Reaction non (i) Gr = (Gf)product – (Gf)reactant
spontaneous
At low temp., (ii) Hr = (Hf)product – (Hf)reactant
H Non (iii)Sr = (Sf)product – (Sf)reactant
when T <
S spontaneous
G = + ve
+ ve + ve
At high temp.,
H
when T > Spontaneous
S
G = – ve
At low temp.,
H
– ve – ve when T < , Spontaneous
S
G = –ve
09.16 kJ