Scribd
Upload
15 views6 pages

Chem Thermo Gist

The document discusses key concepts in thermodynamics, including extensive and intensive properties, work done during expansion and compression, and the relationships between internal energy, enthalpy, and entropy. It covers isothermal and adiabatic processes, the first and second laws of thermodynamics, and the implications of these laws for chemical reactions and phase transitions. Additionally, it introduces Gibbs free energy and its significance in determining spontaneity and equilibrium in chemical systems.

Uploaded by

f20240658
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
Available Formats
Download as PDF, TXT or read online on Scribd
15 views6 pages

Chem Thermo Gist

The document discusses key concepts in thermodynamics, including extensive and intensive properties, work done during expansion and compression, and the relationships between internal energy, enthalpy, and entropy. It covers isothermal and adiabatic processes, the first and second laws of thermodynamics, and the implications of these laws for chemical reactions and phase transitions. Additionally, it introduces Gibbs free energy and its significance in determining spontaneity and equilibrium in chemical systems.

Uploaded by

f20240658
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
Available Formats
Download as PDF, TXT or read online on Scribd
You are on page 1/ 6

Thermodynamics

Extensive Property: A property that depends on the amount of the substance (matter) in the sample. e.g.,
mass, volume.
Intensive property: A property that is independent of the amount of the substance (matter) in the sample.
e.g., pressure, temperature, density.
The work done when a system expands (work of expansion) against an opposing pressure. W = -PexV
Expansion against zero external pressure (free expansion): W = 0.
Free expansion is an irreversible process.
Total work of compression w = +Pex V

Isothermal Reversible work: (A perfect gas)


Irreversible work: w = -pf (Vf – Vi )
W 0, work done by the system. W  0, work is done on the system.
U = w + q
Isothermal expansion of a perfect gas :  U = 0 q = -w
dU = dq at constant volume.
CV = dqv/dT closed system in eqm., P-V work only..
When CV is independent of temperature then, U = CV(Tf – Ti) i.e. U = CV T
Tf
For a finite change, U =  CV dT
Ti
H = U + pV
dH = dU + PdV + VdP
For a system open to atmosphere or in mechanical equilibrium with surroundings
dH = dq + VdP dH = dq , at constant pressure or, H = qp , at constant pressure

Hm = Um + pVm = Um + RT for a perfect gas.

CP = dqp/dT or CP = (H/T)P, closed system in eqm., PV work only


Tf When CP is independent of temperature then, H = CP(Tf – Ti)
For a finite change,
H =  CP dT i.e. H = CP T
Ti
Kirchhoff’s Law: r(T2) = r(T1) +  rCpdT or   (T ) +  C
r

1 r p
(T −T ),
2 1 if rCp constant over the
temperature range.
Perfect gas CP,m – CV,m = R
At very low temperatures non metallic solids Cp,m = aT3
For an isolated system, U = 0
Isothermal expansion of a perfect gas. U = 0, i.e. q = -w.
For Isothermal Free Expansion, U = 0 (perfect gas) and w = 0, q = 0 no influx of energy as heat when perfect gas expands
isothermally against zero pressure.
For Isothermal Reversible Expansion of a perfect gas. q = nRTln(Vf/Vi), q0
A reaction in a container of constant volume, The system can do no expansion work. Therefore, w = 0; Therefore, U = q
So, U = qv , V represents that volume is constant.
Adiabatic expansion/compression of a gas wad = U = Cv T.
This equation is applicable to any adiabatic expansion or compression of a gas. Applicable for reversible or irreversible
processes, since U is path-independent
Irreversible process, dS  0 ; Reversible process, dS = 0
S = qrev /T for a closed system undergoing an infinitesimal reversible change.
qrev = the heat that is transferred when the process is carried out reversibly at a constant temperature.

Isothermal process S=nR lnVf/Vi Entropy Change with volume

Stotal = Ssys + Ssurr ≥ 0 (‘>’for irreversible process and ‘=’ for reversible process)
𝒅𝒒
Clausius Inequality: 𝒅𝑺𝒔𝒚𝒔 ≥ 𝑻
The entropy change accompanying heating Entropy change: S = C ln (Tf /Ti) C: heat capacity of the system.
Entropy Change with Temperature S = CV ln(Tf /Ti) Reversible Heat Transfer at Constant Volume:

The higher the heat capacity of the substance, the greater is S for a given rise in temperature.
Tf
When Cv varies with temperature In these cases, S =  (CVdT /T)
Ti
Entropy change for Phase Transitions fusS = fusH/Tf vapS = vapH/Tb

Trouton’s Rule vapS = vapH/Tb


Entropy Changes in Surroundings: For the reversible, isothermal expansion : Ssur = qsur,rev/T

Entropy Change in Surroundings: Free Expansion U = 0 and w = 0; q = 0.


Since there is no change in the surroundings,
Third Law S = S(T) – S(0) S(0) = 0 for perfectly crystalline substances.

Boltzmann’s entropy formula: S = k lnW where W is the number of ways a molecules can be arranged/oriented
Sm = molar residual entropy = NAk ln W = R ln W
rS° = iS°im (products) − iS°im (reactants)
G < 0 for spontaneous process at constant T and P
G   − S Also, at constant T and p, G = −T(S)tot . and G is minimum at equilibrium
Molar Gibbs energy, Gm= G/n
dG = − SdT + Vdp

(Gm/p)T = Vm and (Gm/T)p = − Sm


Gm = Vmp, Good approximation for condensed matter, Vm almost independent of P.
Gm= − SmT, Assuming that Sm remains constant in the Temp range

Integrating from standard pressure p° to desired pressure p, Gm(p) = Gm(p°) + RT ln(p/p°) = Gm°(T) + RT ln(p/p°)
ΔGm = ∫ Vmdp
• At const. T & P, dG = Σμjdnj, where μj = (G/nj)T,P,nji
• G = Σμjnj with μj the chemical potential of j at a given T&P and composition.
• For a pure substance μ = Gm
μ = μj° (T) + RT ln aj where aj is called the activity of j, and is a function of T, P, and composition. For a
perfect gas mixture, aj = Pj/P°
G = {2 NH3 − (N2 + 3 H2)} n ie., (G/n)T,p = {2 NH3 − (N2 + 3 H2)} = rG, for the formation of ammonia
rG < 0 Spontaneous →
At equilibrium, rG = 0, or
rG > 0 Spontaneous 
At equilibrium, (G/n)T,peq = rG eq = 0 rG = − RT ln Qeq = − RT {(aCc aDd)/(aAa aBb)}eq
rG= −RT ln K, at equilibrium, Q = K, Equilibrium constant
rG = rG + RT ln Q
rG = rH − T rS rG = RT ln(Q/K)

You might also like