A calorimetric and thermodynamic
investigation of two magnesium
phosphates, MgHPO4·3H2O(cr) and MgKPO4·6H2O(cr), was undertaken. The synthesis of
both phases was performed from magnesium chloride and potassium phosphate
solutions at room temperature. The synthetic products were characterized
by powder X-ray diffraction and X-ray fluorescence methods. The enthalpies
of formation of both phases were determined using hydrofluoric acid
solution calorimetry giving Δf
H
m
o(T = 298.15 K, MgHPO4·3H2O,cr) = −2595
± 3 kJ mol–1 and Δf
H
m
o(T = 298.15 K, MgKPO4·6H2O,cr) = −3718 ± 3 kJ mol–1. The low-temperature
heat capacity, C
p,m
o, was measured using adiabatic
calorimetry from T = 6.1 to 324.6 K for MgHPO4·3H2O(cr) and from T = 5.9
to 329.0 K for MgKPO4·6H2O(cr). Using these C
p,m
o(T) data, the third law entropy
at T = 298.15 K, S
m
o, is calculated as 212.9 ±
1.5 J K–1 mol–1 for MgHPO4·3H2O(cr) and 352.7 ± 2.1 J K–1 mol–1 for MgKPO4·6H2O(cr). These new experimental results, together with literature data,
are used to calculate the Gibbs free energy of formation, Δf
G
m
o, for both phases, giving Δf
G
m
o(=298.15 K, MgHPO4·3H2O,cr) = −2292
± 4 kJ mol–1·and Δf
G
m(T = 298.15 K, MgKPO4·6H2O,cr) = −3248 ± 4 kJ mol–1. Smoothed C
p,m
o(T) values between
0 and 320 K are presented, along with the values for S
m
o and the
functions [H
m
o(T) – H
m
o(0)] and
[G
m
o(T) – H
m
o(0)], for both
phases.