Derive the van't Hoff equation,

dlnKdT=ΔH°RT2

which gives the dependence of the equilibrium constant on temperature." Here H°is the enthalpy change of the reaction, for pure substances in their standard states (1 bar pressure for gases). Notice that if H°is positive (loosely speaking, if the reaction requires the absorption of heat), then higher temperature makes the reaction tend more to the right, as you might expect. Often you can neglect the temperature dependence ofH°; solve the equation in this case to obtain

lnKT2-lnKT1=ΔH°R1T1-1T2

Short Answer

Expert verified

Hence the equation is derived.

Step by step solution

01

Given information

Vant Hoff's equation:

dlnKdT=ΔH°RT2
02

Explanation

The equilibrium constant in chemical reactions is given by:

K=e-ΔG°/RT(1)

Where

ΔG°is the Gibbs free energy:

Taking log on both sides

ln(K)=-ΔG°RT

Differentiate both sides with respect to T

ddT(ln(K))=-1RTdΔG°dT+ΔG°RT2(2)

Change in free Gibbs energy

dG=U-SdT+μdN

At constant N,dN=0

dGdT=-S

For standard Gibbs free energy, we have

dG°dT=-S°

Taking difference, we get

dΔG°dT=-ΔS°

Substitute into (2), to get

ddT(ln(K))=ΔS°RT+ΔG°RT2(3)

The Gibbs free energy is:

G=H-TS

At constant temperature, the standard change

ΔG°=ΔH°-TΔS°

Substitute into (3)

ddT(ln(K))=ΔS°RT+ΔH°-TΔS°RT2ddT(ln(K))=ΔS°RT+ΔH°RT2-ΔS°RTddT(ln(K))=ΔH°RT2

03

Explanation

Now that we have separated the variables, such as temperature in the RHS and natural logarithm in the LHS, we must integrate this equation.

dln(K)=ΔH°RT2dT

Integrate both sides from T1toT2

T1T2dln(K)=T1T2ΔH°RT2dT[ln(K)]T1T2=-ΔH°RT°T1T2lnKT2-lnKT1=ΔH°R1T1-1T2

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