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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Most popular questions from this chapter

Use the result of the previous problem to estimate the equilibrium constant of the reactionN2+3H22NH3at 500° C, using only the room- temperature data at the back of this book. Compare your result to the actual value of K at 500° C quoted in the text.

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(a) Imagine making an infinitesimal change in the current in the wire, resulting in infinitesimal changes in B, M, and H. Use Faraday's law to show that the work required (from the power supply) to accomplish this change is Wtotal=VHdB. (Neglect the resistance of the wire.)

(b) Rewrite the result of part (a) in terms of Hand M, then subtract off the work that would be required even if the specimen were not present. If we define W, the work done on the system, to be what's left, show that W=μ0HdM.

(c) What is the thermodynamic identity for this system? (Include magnetic work but not mechanical work or particle flow.)

(d) How would you define analogues of the enthalpy and Gibbs free energy for a magnetic system? (The Helmholtz free energy is defined in the same way as for a mechanical system.) Derive the thermodynamic identities for each of these quantities, and discuss their interpretations.

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Calculate the Helmholtz free energy of a van der Waals fluid, up to an undetermined function of temperature as in equation5.56. Using reduced variables, carefully plot the Helmholtz free energy (in units of NkTc) as a function of volume for T/Tc=0.8Identify the two points on the graph corresponding to the liquid and gas at the vapor pressure. (If you haven't worked the preceding problem, just read the appropriate values off Figure5.23.) Then prove that the Helmholtz free energy of a combination of these two states (part liquid, part gas) can be represented by a straight line connecting these two points on the graph. Explain why the combination is more stable, at a given volume, than the homogeneous state represented by the original curve, and describe how you could have determined the two transition volumes directly from the graph of F.

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