Thermodynamics

Basic
text Terminology:
• System: Part of universe under observation
o Open: exchange of energy + matter with surroundings
o Closed: exchange of only energy
o Isolated: no exchange of energy or matter
• Universe: Anything other than system
• Boundary: Anything that separates the system and surrounding
o Real: Can be seen with eyes
o Imaginary: can't be seen
o Diathermic: allows passage of heat
o Adiabatic: doesn’t allow passage of heat
• Extensive Property: properties of system whose values change on changing the
amount of substance in system, otherwise intensive.
o Division of extensive properties = intensive prop.
o Ext. Properties expressed per unit vol/mol/mass = intensive prop.
• State Parameters: variables that define the state of a system (P,V,n,T)
o To change the state of system, S.P. needs to be changed
• State Function: value only depends on initial and final state of system (path
independent).
• Path Function: value depends on initial and final state- but path dependent
o Eg: Heat (q) and Work (W)

Thermodynamic Processes: Heat [q]

• Isochoric: V is constant • Mode of transfer of energy
o Follows Gay Loussac’s b/w sys. and surr.
Law • Heat flows due to T diff.
• Isobaric: P is constant • High T to Low T
o Follows Charles’ Law • If system absorbs heat, q > 0
• Isothermal: T is constant • If system releases heat, q < 0
o Follows Boyle’s Law
• Adiabatic: no heat exchange
b/w system and surroundings
Work [W]
o Basically q = 0
• Mode of transfer of energy
• Cyclic: System returns to initial
b/w sys. and surr.
state after lot of steps
• Expansion = W done by sys.
o W<0
• Compression: W done by
Heat Capacity [c] surr.
• Amount of heat required to o W>0
𝑣
raise the T of the substance by 1 • 𝑤 = − ∫𝑣 2 𝑃𝑒𝑥𝑡 ⅆ𝑣
1
degree. • 𝑤𝑖 = 𝑃𝑒𝑥𝑡 𝛥𝑉
ⅆ𝑞
• 𝑐=
ⅆ𝑇
• 𝑞 = 𝑐𝛥𝑇
• Specific heat capacity (s) = c/m Molar Heat Capacity [Cm]
• Cm = c/M
te
Internal Energy [U or E] 1st Law of Thermodynamics
• Sum all possible energies • Energy conservation
present in system • Change in system = change in
• State function internal energy
• U = KE + PE (for real gas) o Heat goes in/out of sys.
• U = f(V.T) o Work is done to/by the
• U = KE (ideal gas) sys.
• U = f(T) • Math Ex: ΔU = q + W
• ΔU = nCvΔT = Qv

Relation b/w H and U

Enthalpy [H] • ΔH = ΔU + ΔnRT [n is of gases
• Heat absorbed or released at only]
constant pressure
• Enthalpy is sum of U and P-V
work Isothermal Process:
• H = f(P,T) for RG
• q = -W
• H = f(T) for IG
• During compression: heat is
• U + PV = H
released by sys
• ΔH = q
• During expansion: heat is
• ΔH = nCpΔT = Qp
absorbed by sys

Adiabatic Process:
• Q=W
• During compression:
heating of sys
• During expansion: cooling of
sys
Free expansion
• Expansion against P = 0
• Isothermal: q = 0
• Adiabatic: also isothermal
Efficiency of Cyclic Process:
• Area enclosed by loop / area
under curve
Cyclic Process:
• Initial State = Final State
• Δ(State Function) = 0
• Thus q(net) = -W(net)
• Area enclosed by loop in P-W
graph = | W |
o Clockwise loop: W < 0
o Anti-clockwise loop: W
>0

Entropy [S] Gibbs Free Energy

• Measure of disorder or • ΔG = ΔH - TΔS
unavailable energy • If ΔG < 0 = Spontaneous
• Enthropy of [Crystalline sol. < • If ΔG > 0 = Not-spontaneous
Amorphous Sol. < Liquid < Gas]
• More atoms = more entropy
• Δs = q/T (where q is reversible)