Lattice Energies of Phosphonium Bromide and Iodide

and the Proton Affinity of Bhosphine

BY T. C. WADDINGTON
School of Molecular Sciences, The University of Warwick
Received 1st June, 1965
The lattice energies of phosphonium bromide and iodide have been calculated. Together with
the enthalpies of formation of the salts and that of phosphine, they have been used to obtain a value
of 194-5&5 kcal mole-1 for the absolute proton affinity of phosphine. This value is higher than
that of the water molecule, and indicates that the driving force in the displacement of phosphine
from phosphonium salts in aqueous solution is not the increased binding energy of the proton
but the greater hydration energy of the hydroxium ion.
Few proton afbities of neutral molecules are known. From the lattice energies
of the ammonium halides 1 and other thermochemical data 2, 3 the proton affinity
of ammonia has been calculated 4 to be 209 kcal mole-1. A less reliable value of
the proton affinity of the water molecule of 182 kcal mole-1 has been obtained from
the enthalpy of formation of hydroxonium perchlorate, AH; H30+ClOi(s), and
the assumption that the lattice energies of ammonium and hydroxonium perchlorate
are the same.5 The crystal structures of phosphonium bromide and iodide are
known and so are the enthalpies of formation, AH;! PH4Br(s) and AH; PH4T(s)
and of phosphine, AH;! PH3(g) so that the thermochemical cycle
u + 2RT
P H4 X( s MP H, + ( d + x-(d
AH;PH~X f 4 'PH,
P(s) + 2HZ + *Xz
PH3 + 3H2 -l- 3X,--PH,(d + H( d 3- X(g)
PpH3 = - U ~ H~ X - ~ R T + I - E ~ ~ ~ ~ H, + ~ ~ , , $ A H; : P H~ - A H; : PH4X,
PH3b) + !3 + (9) + x - (9)
-AH;PH~ f 4 -Z+Ex
-4DH2
- 30x2
gives the relationship
(1)
or
PpHs = - UPH~X- ~RT- ~AH; H+(g)+AH;1 X-(g)+AH; PH3 - AH; PH4X, (2)
where PPH, is the proton affinity of phosphine, I is the ionization potential of the
hydrogen atom, EX is the electron affinity of the X atom, DH, and Dx, are the
bond dissociation energies of H2 and X2 respectively, and AH; X-(g) = 3Dx2- Ex
and AH; Hf = I++&,.
CALCULATI ON OF THE LATTICE ENERGIES
CRYSTAL STRUCTURE
Both PH4Br 6 and PH4I 7 have a tetragonal unit cell, space group Pnmm ( Di h)
with 2 molecules in the unit cell. The dimensions of the unit cell are, for PHdBr,
2652
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T. C. WADDINGTON 2653
a0 = 6.042 A, co = 4.378 A and for PH41, a0 = 6.34 A, co = 4.62 A. The phos-
phorus and halogen atoms are in the following special positions :
P; 000: 330 : I ; o*u; $0U,
with u = 0.42 for PH4Br and 0.40 for PH41. Thus, each halide ion is surrounded
by 8 phosphonium ions, 4 slightly closer than the other 4, and each phosphonium
ion is similarly surrounded by 8 halide ions. The distances are in PH4Br, 4 nearest
neighbours at 3.536 A and 4 at 3-945 A, and in PH41, 4 nearest neighbours at 3.67 A
and 4 at 4.21 A.
LATTICE ENERGY
The expression developed by Ladd and Lee 8 was used, since it was considered
that this would be more reliable than attempting to assign a Huggins basic radius 9
to the phosphonium ion. It is
Here N is Avogadro's number, M the Madelung constant of the lattice, ro the dis-
tance between nearest neighbours, p a constant with the dimensions of length, taken
to be 0.345 x 10-8 cm. By comparison with the alkali metal halides,g C is a summa-
tion constant like the Madelung constant, but for the dispersion forces in the lattice.
M, the Madelung constant, was calculated by the approximate method of
Templeton,lo and values of 1.674, based on YO = 3.536, for PH4Br and 1.652, based
on ro = 3-670, for PH41 were obtained. These lead to values of the first term in
the Ladd and Lee expression of 141-5 kcal mole-1 for PH4Br and 135.0 kcal mole-1
for PH4I. From similar cases quoted by Templeton 10 the error introduced into
the Madelung constant leads to an error of less than 5 1 kcal mole-1 in the first
term. The inaccuracies in the deterininations of the crystal parameters, particularly
u, probably lead to another uncertainty of +2 kcal mole-1.
For the next term, which corresponds to a correction for the dispersion energy,
C is given by
Uo = (NMe2/ r, )(l - p/ ro) + (NAC/rg)( 1 - 6p/ro) - (9/4)Nkv.
(3
where
cI1 = + E ~ ~ I : ; c22 = ~ E ~ C I : and c12 = 2 ~ ~ & ~ a ~ a , / 3 ( & ~ + E ~ ) . (5a, 6, c)
!1 and 82 are the oscillator energies of the ions and a1 and a2 are their polanza-
bilities. s6and S$ are summations over the whole lattice. Since the whole of this
term is second order and since the phosphonium halide lattices can be regarded
as distorted CsCl lattices, & and S,l are taken as half the Cscl vahes.11 & = 8-708
and S,l = 3.5445, for each of the two sets of nearest neighbours of the phosphonium
ion. The values aBr = 4.49 x 10-24 cm3, EBr = 13.8 x 1012 erg molecule-1 and
a1 = 6.66 x 10-24 cm3, EI = 12.0 x 1012 erg niolecule-1 are taken from Bleick's
paper 1 on the lattice energies of the ammonium halides. ap~; t , the polarizability
of the phosphoniurn ion, in the absence of any other data is calculated by assuming
~~B: / c I NH; ~ = QK+/CCN~+. Values 1 of UNH; = 1-70, LXK+ = 0-844 and UN,+ = 0.182 x
10-24 cm3 lead to a value of 7.9 x 10-24 61113 for ~IPH;. Bleick 1 took the value of
E for the NH,S ion to be 90 % of the ionization potential and calculated I from the
relationship INH:/IcH, = INa+/lNe. This type of proportional relationship is in-
accurate but in the absence of any other data is the best available. The relationships
of 20.9, 28.7 and 24.2 eV for IPH+. A value of 25 eV is adopted for ZPH; and 6
IPH:/INH4+ JK+/INa+, IPI!~/~SIH, hH$/IcE4 and IPHt/lSiH, = IK+/IA yield Values
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2654 LATTICE! ENERGIES
taken to be 22.5 eV. These magnitudes lead to values of 6.6 kcal mole-1 for PH4Br
and 6.7 kcal mole-1 for PH41 as the second terms in the expression for the lattice
energy. The percentage error in these second terms is high. The greatest con-
tribution to the error comes from the inaccuracy in the value of IPH;, which may
be as great as 20 %. Taking the total percentage error as about 30 %, these second
terms are uncertain by about +2 kcal mole-1.
The last term, (9/4)Nhv, the zero-point energy, can only be estimated roughly
but since this term is very small no great inaccuracy is produced in the total lattice
energy. For phosphonium bromide and iodide it is taken to be
(9/4)NhVP,,, = (M,,,x/MP,,x)(9/4)Nhv,,,,, (6)
where MNII, X and MPH,X are the molecular weights of NH4X and PH4X respectively.
This leads to values of 0.8 kcal mole-1 and 0.5 kcal mole-1 respectively for PH4Br
and PH4I. These terms give total lattice energies of 147.3 +5 kcal mole-1 for
P&Br and 141 *2 1.5 kcal mole-1 for PH&
DISCUSSION
From eqn. (2) we find
PH4Br PHJ ref.
- GT&x - 147.3 - 141.2
-2RT - 1.2 - 1.2
+ AH; H+(g) + 367.1 + 367.1 2
+ AH; X-(g) - 54.9 - 49.1 3
+ PH3W + 2 2 + 2.2 2
- AH; PH~X(S) + 29.5 + 15.8 2
Thus we can assign a value of 194.5+5 kcal mole-1 to the absolute proton
affinity of phosphine. This compares with a value of 209 kcal mole-1 for am-
monia, based on the lattice energy calculations of Bleick and a value of 182 kcal
mole-1 for the water molecule, based upon some less reliable calculatioiis of
Sherman.5 The value of PPH, = 194-5 kcal mole-1 means that the gas-phase
reaction
PH,+(d+H,O(d = PH3(d+H3O+(d (7)
is endothermic by about 12.5 kcal mole-1 and that the equilibrium would lie to the
left. However, we know that the reaction
PH,+(ad+H,O(ad = PH, (d+H, O+(ad (8)
proceeds to the right. The driving force for this reaction must be the diEereiice in
hydration energies of the hydroxium and phosphonium ions. Using Halliwell
and Nyburgs 12 value, 261 kcal mole-1 for the absolute hydration energy of the
proton, H+, and the value for the proton affinity of water 5 PEI,O we obtain 89 kcal
mole-1 for the absolute hydration energy of the hydroxonium ion. An extrapolation,
based on an approximate crystal radius of 1.77 for the phosphonium ion, gives
it an absolute hydration energy of about 60 kcal mole-1. Using a value of 10.6
kcal mole-1 for the latent heat of vaporization of water, eqn. (8) has an enthalpy
of reaction of about - 6 kcal mole-1.
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T. C . WADDI NGTON 2655
1 Bleick, J. Chem. Physics, 1934, 2, 160.
2 Rossini et al., US. Bur. Stmd., circ. 500, 1952.
3 Pritchard, Chem. Rev., 1953, 52, 529.
4 Waddington, in Recent Advances in Inorganic and Radiochemistry, vol. 1, 1959.
5 Sherman, Chem. Rev., 1932, 11,93.
6 Dickinson, J. Amer. Clzem. SOC., 1922, 44, 1489.
7 Scatturin, Bellon and Frasson, Atti. Inst. Veneto Sci. Lettere Arti, Classe Sci. Mat. Nat.,
8 Ladd and Lee, Trans. Faraday Soc., 1958,54, 34.
9 Huggins, J. Chem. Physics, 1937, 5, 143.
10 Teinpleton, J. Chem. Physics, 1953, 21, 2097.
11 Lennard-Jones and Ingham, Pmc. Roy. SOC. A, 1925,107, 636.
12 Halliwell and Nyburg, Trans. Faraduy Suc., 1963, 59, 1 126.
1955-6, 114, 67.
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