65673556ebbd5a00188e56ad - ## - Thermodynamics Short N - 231217 - 235549
65673556ebbd5a00188e56ad - ## - Thermodynamics Short N - 231217 - 235549
65673556ebbd5a00188e56ad - ## - Thermodynamics Short N - 231217 - 235549
6 Thermodynamics
Properties which depends only on initial & final state of system &
not on process or path. e.g. U, H, S, G, etc.
SIGN CONVENTION
PATH FUNCTION
Depends on path or process. e.g. work, heat.
THERMODYNAMIC PROPERTIES
1. Intensive: Independent of amount of substance, e.g. T,P Gas
viscosity, specific heat capacity, density, Boiling point, w = +ve w = –ve
freezing point, etc. Compression Expansion
2. Extensive: Depend upon amount of substances, e.g. mass,
volume, energy, entropy, enthalpy, internal energy, etc. Heat absorbed by the system = q (+ve)
Heat evolved by the system = q (–ve)
PROCESSES Work done on the system = w (+ve)
1. Isothermal: Temperature constant. Work done by the system = w (–ve)
2. Isobaric: Pressure constant.
3. Isochoric: volume constant. INTERNAL ENERGY (E & U)
4. Adiabatic: Heat change constant. Every system having some quantity of matter is associated with a
5. Cyclic: Initial & final state of system are same. definite amount of energy called internal energy.
Reversible process Irreversible process U = UKinetic + UPotential + UElectronic + Unuclear + ........
Slow process Fast process
At any time system No equilibrium between FIRST LAW OF THERMODYNAMICS
and surrounding are in system and surrounding Law of conservation of energy
equilibrium. Psys = Psurr ± DP
DU = q + W
Psys = Psurr ± dP
ENTHALPY
H = U + PV, DH = DU + (Dng) RT
V2 V P1
w = –nRT ln q = nRT ln 2
Reversible V1 V1
P (atm)
P2
isothermal P P
= –nRT ln 1 q = nRT ln 1
P2 P2
V1 V2
P1
q=0
Reversible w = nCV(T2–T1) Isotherm
PVg = constant Adiabatic
P (atm)
adiabatic P V –PV P2
= 2 2 1 1 TVg–1 = constant
process γ –1
TP1–g/g = constant
V1 V2
P
W Chemical Thermodynamics and Energetics 15
THERMOCHEMISTRY 4. Enthalpy of hydration: The enthalpy change during the
hydration of 1 mole of anhydrous salt to a specific hydrate.
Bond Enthalpy
5. Enthalpy of neutralization (DHneut) Always exothermic:
Average amount of enthalpy required to dissociate one mole
Change in enthalpy when one gram equivalent of an acid is
gaseous bond into separate gaseous atoms.
completely neutralized by one g-equivalent of a base in dilute
DrH = (Sum of bond enthalpy of gaseous reactant) – (Sum of bond
solution.
enthalpy of gaseous product)
SA + SB → salt + water ; DH°neut
Resonance Energy H+(aq) + OH–(aq) → H2O(l) ; DH = –13.7 kCal eq–1 = –57.3 kJ eq–1
∆H °resonance = DfH° (experimental) – DfH° (calculated) In case of weak acid/ base or both |DHN° | < 13.7 Kcal/eq–1 and
= DCH° (calculated) – DCH° (experimental) the difference is enthalpy of ionisation of weak species except
in case of HF when |DHN| > 13.7 Kcal/eq–1 due to hydration
Enthalpy Change of F–.
DH° = ∑H° (products) – ∑H° (reactants) If in a reaction heat of reactant & products are given then heat
1. Enthalpy of reaction: The enthalpy change accompanying of that reaction can be measured as follows:
a chemical reaction when the number of moles of reactants (a) For heat of combustion & for bond enthalpy
reacts to give the products as given by the balanced chemical
equation. DrH = Σ(DHC)reactant – Σ (DHC)product
2. Enthalpy of Combustion (DcH°): The amount of heat change (b) For heat of formation
when 1 mole of substance is completely burnt in excess of
DrH = Σ(DHf)product – Σ (DHf)reactant
oxygen or air. DcH° is always negative.
3. Enthalpy of solution: The enthalpy change when one mole Hess’s Law: The enthalpy change in a particular reaction is the
of a substance is dissolved in large excess of solvent so that same whether the reaction take place in one step or in a number
further dilution does not give any further enthalpy change. of steps.