II

Egypt. J. Sol, Vof.(14), No. (1), (l99l)

Specific heat capacity, thermal conductivity

and thermal diffusivity of ammonium nitrate
in the temperature interval 293 - 433 K
A_"- El-Sbll~, A.M. Abousehfy4', K.K. Tahoon S.Taha t and G. AttJa t

*t

PIrysics /)qH1r1mm4 Focuhy 0/ Sdmu, AJ...A.th.oT UrWtnity. N_ City, Cairo, Egypt.

I Plrpks IXparrmmt, Foculry 0/ Girls, AJ....Uhar u:~.iw:nity. Coiro, E~pt.
t Physics Dtparrmmr. Focuhy ofEducatioo, EJ-Ft:ryOUl'I1, Cairo Univmity.

Specific beal capacity (CJ. Ihennal conductivity (A.)and thermal diffusiviry (a> of Altl
monium Nitrale are roe!sum:t in the temperalure rant;e 293 to 413K. Specific beal
capacity shOW$ three transilion points al 3S8.K, 398K and 404K. The mech!nism of beal
lransrer is discussed and il w.:.:. round IMt the main roech.anism of heat lransfer is due
to pboDODS only.

In trod action:

AmnlO{Lium nitrate. is a compound consisting of complex ions of two types:

tetr3.hedral NH; cations and flat NO; anions. These ions are coupled not only by
electrostatic forces but also by hydrogen be-nds in the crystal. Crystalline NH4N03
has six stable modifications [1], which differ in structure in ion mobility, and in ion
disorder in the lattice.
Phase I, II and III have disorder of ions of both types, whereas N, V and VI dif
ions. The room tern.
fer in symmetry and in the orientational motions of tbe
perature phase IV is orthorhombic with a centric space group P (0 13-. and twd
.
]
ronn 2lY'
molecules per umt cell {2,3 . At temperatures below 257K, the crystal transforms to
another phase V. X-ray results [4] suggested that the crystal structure undergoes
noncentric tetragonal in which the NO; grO\;ps :lre involved in an approximately 9Q'>
reorientation about the C-axis and one-half of them flip over about axis perpen
dicular to the C-axis. The space group of phase V; is P42(~ with Z ::; 8. The NO;
groups occupy two non-equivalent sets of C t sites while the H4 groups occupy four
non-equivalent sets of C~ sites. Both kinds d ions are aligned in columns along the
C-axis which is a polar 3XlS.

NH:

Measuring method:
The pulse method for measuring the thermal diffusiviry (a) and specific heat
capacity (C~ was used 151. The thermal diffusiviry can be calculated by:
12
a == 0.139 _
m2.s~1
to.5
where t05 is the time required for the lower su,;ace of the sample to reach
half-ma.ximum in its small temperature rise, and I is tf,': thickness of the sample.
n.e specific heat capacity (C~ can be determine..:! by the relation

Cp == qIMTm

A.A. FJ-Sharica"l. et al
where q
is the power dissipated through through the sample
M is the mass of the sample
Tm is (he maximum temperature rise.
The power dissipated through the sample can be measured by using a standard
material with known specific beat.
The thermaJ conductivity Acan be calculated from the relation

A=

dCp 2

where d is the density of the sample.

The beat losses by radiation from the boundaries of the sample were taken in
considerations. The ratio between the diameter of tbe sample and the thickness can
be chosen [5]. The experimentaJ errors of these properties did not exceed 2% for
heat capacity Cp' 3% for thermal ditfusivity and 5% for thermal conductivity.

Results and D1saJsslon:

1. Specific heat capadlJ

60 -

l<:

0'.

l<:

....
S:!

i.O

Q.

C)'I
'..
3CQ

3S0
T,K

Fig.1.

Ihe .marion of specific hear capacityvvith temperature for Ammocium Nitrate.

Fig.(l) shows the variation of sp.;dfic heat capacity C 9rith temperature in the
temperature range 293 up to 433K. It was (ound that C d~ no! change with tem
perature in the orthorhombic phase from 293 to 358K The results obey Debye
theory of specific heat. In the temperature 358 to 398K, the sample NH4N0 3 change
to tetragonal structure which has a unit cell dimensions a = b = 5.74 A and c = 4.95
A [6]. The variation of the specific heat capacity C with lemperature in the internal
region of the tetragonal phase due 10 the plaoelstructure of N0 3 group causes a
large anisotropy of the polarizability and there are two space groups of this phase

&tpt. J. Sol., Vol.(14), No. (1), (1991)

c!..

namely ~ or
In the tempera ture region the NH;ions are in a nearly free rota
tional state in this phase [7-11]. In the temperature interval 398K up to 404K the
specific Feat also changes with temperature and the material changes to cubic struc
ture. In this phase the nitrate group occupies the centre of the unit cell an.::! the
dimensions are a b =c = 4.4 A Also the variation of the specific heat with tem
perature in this region refers to the nitrate group in this phase is fairly free to rotate,
while the ammonium group are free to rotate. The temperature range of tbe two
phases are summarized as CollO"ilt'S:
Tetragonal
358 to 398 K
Cubic
398 to 404 K
After 4051(, the malerial is melted and changed to liquid state.

2. Thermal conductivitv 1:

",'

1.5

to
0.5

1.50

T. K
Fig.2.

The variation or the Iherm.a.! conductivity ror NH.NO (Ammonium Nitrate) ....i lh lemper.tl ure.
l

The thermal conductivity of ammonium nitrate is shown in Fig.(2). It -was found

that the thermal conductivity decreases as temperature increases. The points of
phase transition also appeared at 385, 398 and 404K. The electronic part of t!::::rmal
conductivity is negligible in the measured temperature range because of the ir::sulat
ing properties of this materiaL The decrease of thermal conductivity i" related to the
decrease of the mean free path of phonons with temperature according (0 the rela
tion [12]
:.

1
where

and

Vv

1'3 Cv VI

is the specific he.2 ( at constant volume

is the velocity of sound
is tbe phonon mean free path

M EhShark.awy. et al

So we can condude that tbe main mechanism of heatlr.lnsfer of Ammonium Nitrate

is due to phonons only.

3.1bepnaJ dilfusivity a:

350

J'i&.3.

..00

1.50

T. K
1"be variation or thermal diffu3iviry with tempera lure Cor Ammonium Nitrolle.

The thermal diffusivity for ammonium nitrate is shown in Fig.(3). It was found
that the thermal diffusivity decreases as temperature increases. This results indicate
that the material is typicaJ insulator. The thermal diffusivity related to the thermal
roDductivity and specific beat capacity by the relation

a = lId Cp
where d is the density of the investigated material.

L
1
3.
4.
5.
'7.
..

LN. Brown and ,,-c. Mclaren; Fmc. R Soc. London SeT., A 266, 329 (1962).

C. W. West; J. Am. ClIent. Soc., 54, 22S6 (1932); Whetstone, J. Acta ~l.. 1,696 (1954).
S. COOk and J.E. Mapes; Acta Crysl... B, 28, 1357 (1m).
SA Hendrick!!, E. PosnJak aDd F.C. Kraa:l; J. Am. CIIem. Soc., 54. 1:166 (1931).
W.J. Parker, R.J. Jtnldnes, c.P. Butkr aocI G.L. Abbol; J. AppI. Phys., 32, 167~1 (1961) .
P. El--Kabbany. Y.llodr aDd G. Said; Phys. SIal. Sol. (a). 63, 3S5 (1981).

R.N. Bnm"D and "-Co Metann; Pmc. Roy. Soc.. (London), A266, 329 (1962).

Y. ShJDD31ct.; J. Phys. Soc., Japan, II. 393 (1956).

.

,. M. R1g:in. R.R. Kn~l and M.M. Pintar; J. Chem. pbys., 56. 2911 (1971).

1(1, R.'l Rkhard and T. ScboUer; Tram. Faraday Soc.. 57, 210(1961).
lL ac. TaIliand B.H. Torr\e;J.Phys. Otem.Solids.l38,l25 (1977).
11 1lP.lJe; Thermal Conductivity, Vol.2, Academic Press, London (1969).