M-1027

J. Chem. Thermodynamics 1979,11, 811-814

The standard enthalpy of formation of

ammonium nitrate and of the nitrate ion
J. D. COX, D. HARROP, and A. J. HEAD
Division of Chemical Standards,
National Physical Laboratory,
Teddington, Middlesex TWll OL W, U.K.

(Received 27 February 1979)

The standard enthalpy of formation of ammonium nitrate in its stable reference state at
298.15 K has been derived from measurements of the energy of combustion of samples of
hydrocarbon oil and polyethene sheet in the presence of ammonium nitrate. Under the
conditions chosen, the last substance decomposed to N,(g), O,(g), and HaO(l); the only
significant by-product found was HNOB.nHzO. Special care was devoted to preparation
of the NH4N03 sample in its stable state (crystalline form IV), free of water. Combination
of the resulting value of AfH” with recent data on the enthalpies of solution and dilution of
NHaNO,(cr, IV), together with key values from the CODATA compilation, gave
A#(NOg, as) = -(206.81 cir.0.41) kJ mol-I.

1. Introduction
The CODATA Task Group on Key Values for Thermodynamics has shown(‘) that
the true vaIue of A&?“(NO;, aq, 298.15 K) probably lies between -206.4 and
-208.0 kJ mol-I, which is the range of credible values derived from various thermo-
chemical cycles. This spread of values is wider than is desirable for such an important
thermodynamic quantity, and in consequencethe Task Group has encouraged more
experimental work on pertinent nitrogen species.A key compound in several thermo-
chemical cycles is ammonium nitrate, in both its normal reference state and the
infinitely dilute aqueous state, at 298.15 K. New values have been obtained(z*3) for
the enthalpy of solution in water of the crystalline form IV, the stable modification(4)
at 298.15 K; the present paper reports a new value for the standard enthalpy of
formation of ammonium nitrate in the same crystal modification.
Two earlier values(5S6)of A,H’(cr) were derived from measurements of A,U” for
the decomposition reaction :
NH4N03W = NAg) + KU) + 2&W.
This equation is a much simplified representation of the reactions actually studied:
in reality, Becker and Roth(‘) measured the energy of oxygen combustion of paraffin
oil -+ Vaseline in the presence of ammonium nitrate, whilst MCdard and Thomas(6)
measured the energy of oxygen combustion of both nitrobenzene and dinitrotoluene
(mixed isomers) in the presenceof ammonium nitrate. By careful choice of the ratios
812 J. D. COX, D. HARROP, AND A. J. HEAD
between organic substance and ammonium nitrate, the complete combustion of the
former and complete decomposition of the latter were apparently achieved. Indeed,
the agreement between the two setsof calorimetric results, after correction to 298.15 K
and standard states, is reasonable. However, doubts remained concerning the possible
occurrence of undetected by-products of combustion and concerning the exact states
of the respective samples of ammonium nitrate at the time of combustion: were the
samples totally in form IV ?; had the samples absorbed water ?; what was the effect
of immersion of the powdered salt in the organic liquids ? The present work employed
the same basic approach as Becker and RothC5) and Mtdard and Thomas,@j)but
special efforts were made to render our sample of ammonium nitrate anhydrous, to
avoid any subsequent uptake of water, and to avoid contact with the liquid organic
reactant. We were also able to take advantage of recent studies@,3, of ways of pre-
paring ammonium nitrate wholly in crystal form IV; we followed Vanderzee’s
prescription, t3) to give a high probability that his sample, as used in solution experi-
ments, and our sample as used in decomposition experiments, were energetically
identical.

2. Experimental
The organic reactants used in the present work were polyethene film and a hydro-
carbon oil, substantially n-hexadecane. Quantitative determination of the nitrogen,
oxygen, and water produced by decomposition of ammonium nitrate was not feasible;
attention was therefore focussed on detecting the possible by-products, namely
NH:, NO,, in solution, and NO2 and NzO in the bomb gases. For this purpose,
analyses were carried out immediately after the main periods of specially conducted
combustion experiments, to minimize time-dependent reactions of nitrogen oxides.(‘)
NHj’, determined calorimetrically by Nessler’s reagent, gave a response equivalent
to about 0.01 per cent of the NH,NO, taken; however, a blank combustion of
hydrocarbon oil without ammonium nitrate present gave a similar response, so the
apparently positive indication of NHt may have been spurious. NO; was determined
calorimetrically by the sulphanilic acid + a-naphthylamine reaction; about 10 umol
were found after combustion, very similar to the amount found after a combustion
of hydrocarbon oil alone. NOz(g) was determined by discharging the bomb gases
through sodium hydroxide solution, then determining NO; as above; about 1 umol
was generally found, no different from that found after a blank combustion. N20(g)
was sought by measurement of the infrared absorption (at 2224, 1286, and 589 cm-l)
of the bomb gasesafter passagethrough soda-lime and a trap at 195 K into a cell of
21.75 m path length; calibration with synthetic gas mixtures indicated that the N20
content of the bomb gas was less than 1 umol. This amount of N,O(g), like
the amounts of NO,(g) found, was without calorimetric significance. The amount
of NO, found was on the borderline of significance, but since the amount found when
NH,N03 was present initially was the same as the amount found when hydrocarbon
oil alone was burnt, and since no corrections for NO; were made in our earlier
measurements of A&(hydrocarbon oil), a calorimetric correction for NO; in the
combustion experiments with ammonium nitrate was deemed to be unnecessary.
 ENTHALPY OF FORMATION OF NITRATE ION 813
Indeed the only by-product for which a calorimetric correction was made was
HNO, *nH,O, determined by alkali titration. The energy utilized in this correction
was based on the present value of A,H”(NO;, aq), by iterative calculation.
An Analar grade (Hopkin & Williams) of ammonium nitrate was used; it was
stated to contain less than 0.01 mass per cent of non-volatile matter, less than 0.001
mass per cent of insoluble matter and less than 0.008 mass per cent (in toto) of
determined impurities. The crystals were crushed, dried at 385 K for 24 h, pelleted
in a press, and stored over P,O, at 295 K. Pellets were weighed into polyethene bags
made from 0.05 mm film, and heat-sealed. A filled bag was placed in a platinum
crucible; then hydrocarbon oil from a reference stock was weighed in. The crucible
was placed in the gimbal of a platinum-lined and platinum-accoutred rotating-bomb,
whose construction and use have been described,0) 10 cm3 of water were placed in
the bomb, and purified oxygen to 2.0 MPa was introduced. The general calorimetric
procedure was as described,“) except that readings of thermometer resistance were
taken semi-automatically.(9)
The bomb calorimeter was calibrated by combustion of thermochemical-standard
benzoic acid (N.B.S., batch 39i), for which A# has been given(“) as -(26 433.6 f
1.1) J g-l; indistinguishable results were obtained in calibration experiments with or
without rotation of the bomb. The rate of generation of energy by rotation was found
to be 0.12 W.

3. Results
The auxiliary data used in the calculations are summarized in table 1, and the results
of the combustion experiments are given in table 2; it will be seenthat energy deriving
from combustion of hydrocarbon oil (qh) and polyethene (qJ accounted for nearly
90 per cent of the measured energy change (q). Also shown are the energy corrections

TABLE 1. Auxiliary data, for 298.15 K

Substance -A&/J g-l p/g cmp3 cp/J K-l g-l -(&&)/J g-l MPa-I

NH,NO,(cr, IV) - 1.72 1.73 0.025

Hydrocarbon oil (1) 47143.6 f 6.5 0.775 2.08 0.29
Polyethene (s) 46386.7 4~ 14.8 0.92 2.22 0.17

TABLE 2. Energy of decomposition of ammonium nitrate

~4NH,NW/g q/J qfi/J %/J %/J q=s/J -A&/J g-l

1.09981 25511.6 18352.0 4188.3 68.0 21.9 2620.6

1.10894 22074.5 15220.1 3866.7 59.2 19.3 2624.2
1.22118 21837.1 14874.9 3678.7 61.7 19.6 2622.8
1.00354 23736.8 15972.6 5061.6 57.3 20.2 2616.8
1.10479 26061.6 17790.3 5294.9 62.6 22.4 2617.8
0.99091 24853.3 17487.0 4692.0 56.6 21.3 2621.1
Mean : 2620.6
Standard deviation of the mean: 1.2
814 J. D. COX, D. HARROP, AND A. J. HEAD
for formation of nitric acid (& and for reduction to standard states (q,,); the values
in the final column relate to the decomposition reaction written above. Not shown
are the very small corrections for electrical energy of ignition (0.7 J) and energy of
delayed rotation (- 1.5 to - 1.6 J).(*)

4. Discussion
With the s.d.m. of the combustion series werecompounded the corresponding quantities
for the calibrant, the two organic reactants, and the calibration experiments, by the
usual method;@‘) multiplication of the resulting overall s.d.m. by 2 gave the “overall
uncertainty interval” as + 3.9 J g-l. The following quantities (all at 298.15 K) were
then derived: A,U” = -(209.77 _+0.31) kJ mol-I; A,H” = -(206.05 & 0.31) kJ
mol-’ ; AfH”(NH,NO,, cr, IV) = -(365.61 _+0.32) kJ mol-I. In the derivation of
the last quantity, the CODATA value(12)for dl,H”(H20, 1)was employed. Evaluation
of AfH”(NO,, aq) required values of A,,H”(NH,NO,, cr, IV, coH,O) and 11,H”
(NH:, as>, which were taken from Vanderzee et aZ.c3)and CODATA(12) respectively,
giving
A,H”(NO;, aq) = -(206.81 + 0.41) kJ mol-I.
This value accords well with that derived from equilibrium measurements on the
decomposition of NH,NO,(cr), but much less well with that derived from equilibrium
measurements on the decomposition of HN03(g). (I) The value reported here for
4U“ is consistent with Becker and Roth’s and Mtdard and Thomas’ values,(5*6)
but is considered to be more firmly based. Moreover, the near-certainty that our
sample of ammonium nitrate and that of Vanderzee et al. had identical specific
enthalpies at 298.15 K permitted combination of thermochemical quantities for
decomposition and solution, measured in separate locations on samples of separate
origin.

REFERENCES
1. Tentative set of key values for thermodynamics.Part VI. CODATA Special Report 4, March
1977.
2. Medvedev,V. A.; Efimov, M. E. ; Cerutti, P. J.; McKay, R. M.; Johnson, L. H. ; Hepler, L. G.
Tlermochimica Acta 1978,23, 87.
3. Vanderzee,C. E.; Waugh, D. H.; Haas, N. C. to be published; Vanderzee,C. E.; Waugh,D. H.;
Haas, N. C.; W&g, D. A. to be published.
4. Stephenson,C. C.; Bentz, D. R.; Stevenson,D. A. J. Am. Chem. Sot. 1955,77,2161.
5. Becker,G.; Roth, W. A. 2. Elektrochemie 1934,40, 836.
MBdard, L.; Thomas, M. Mem. Poudres 1953,35,155.
4: Aleksandrov, Yu. I.; Mikina, V. D.; Novikov, G. A. Tr. Metrol. Inst. SSSR 1969, NO. 111,95.
8. Cox, J. D.; Gundry, H. A.; Head, A. J. Trans. Faraday Sot. 1964,60,653.
9. Fenwick, J. 0.; Harrop, D.; Head, A. J. J. Chem. Thermodynamics 1975,7, 943.
10. Gundry, H. A.; Harrop, D.; Head, A. J.; Lewis, G. B. J. Chem. Thermodynamics 1969, 1, 321.
11. Bjellerup, L. Acta Chem. Scand. 1%1,15, 121.
12. CODATA recommendedkey values for thermodynamics,1977.J. Chem. Thermodynamics 1978,
10,903.