Problems Sheet

Thermodynamics

Recommended lectures: Introduction to Geochemistry, Misra, Chap. 4 – Geochemistry, W.

White, Chap 2.

1. (0.5) If the molar volume of granitic magma is 7 × 10−5 m3, and on crystallizing it
decreases by 10%, compare the work done by magma crystallizing near the top of a
batholith, where the pressure is 0.05 GPa, with magma crystallizing near the base of
the batholith, where the pressure is 0.5 GPa. Be careful of the sign convention.

2. (1.0) From data in the given table and using the definition of entalphy as a function of
heat capacity, determine the enthalpy of formation of kyanite and andalusite at 466 K
and 105 Pa (1 bar). If kyanite were to change into andalusite under these conditions,
what would be the enthalpy of this reaction be? Is the reaction exothermic or endo-
thermic? (Be careful of the sign convention; write the reaction kyanite → andalusite,
then ΔHr is the final enthalpy minus the initial.)

3. (0.5) If entropy is a function of temperature and pressure, that is, S = S(T,P),

a) Write the total differential of S(T,P)
b) Show that the total differential of S(T,P) is given by
✓ ◆
CP
dS = dT ↵V dP
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T
4. (1.0) Convection within the mantle or within a magma chamber causes the thermal
gradient to approach the adiabatic gradient (đQ = 0 and dS = 0). Using the expression
for dS in Problem 3, along with the cyclical rule for partial derivatives show that the
adiabatic gradient is given by:
✓ ◆
@T TV ↵
=
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@P S CP
5. (1.0) The granitic magma in Problem 1 has a molar volume of 7 × 10−5 m3, a molecular
weight of 0.168kg (ρ = 2.4Mgm−3), a coefficient of thermal expansion, α, of 2 × 10−5
K−1, a heat capacity, Cp, of 0.8 kJ kg−1 K−1, and a temperature of 900 °C (1173 K).

a) If magmatic convection has established an adiabatic temperature gradient within the

body, calculate the value of

@T
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@P S

b) Using the fact that any change in pressure depends on depth as dP = ρg dz calculate the
adiabatic temperature gradient, (dT/dz)S, in this convecting body of magma, and
 compare this value with a typical geothermal gradient in the upper continental crust.

6. (1.0) A typical eruption temperature of a basaltic lava is about 1200 C. Assuming that
basaltic magma travels from its source region in the mantle quickly enough so that
negligible heat is lost to wall rocks, calculate the temperature of the magma at a depth
of 40 km. The density of basaltic magma at 1200 C is 2610 kg/m3; the coefficient of
thermal expansion is about 10-4/K. Assume a heat capacity of 850 J/kg-K and that
pressure is related to depth as 1 km= 33 MPa (Surface pressure is 0.1 MPa)