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PEC 8 J366
299
George T. Armstrong
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US DEPARTMENT OF COMMERCE
Z National Bureau of Standards
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THE INSTITUTE FOR BASIC STANDARDS . . . provides the central basis within the United
and consistent system of physical measurements, coordinates that system with the
States for a complete
measurement systems of other nations, and furnishes essential services leading to accurate and uniform
physical measurements throughout the Nation's scientific community, industry, and commerce. This
Institute comprises a series of divisions,each serving a classical subject matter area:
—Applied Mathematics — Electricity —Metrology—Mechanics — Heat—Atomic
Physics Physical —
— — —
Chemistry Radiation Physics Laboratory Astrophysics 2 Radio Standards Laboratory, 2 which
includes Radio Standards Physics and Radio Standards Engineering —
Office of Standard Refer-
ence Data.
THE INSTITUTE FOR MATERIALS RESEARCH conducts materials research and provides
. . .
associated materials services including mainly reference materials and data on the properties of ma-
terials. Beyond its direct interest to the Nation's scientists and engineers, this Institute yields services
which are essential to the advancement of technology in industry and commerce. This Institute is or-
ganized primarily by technical fields:
—Analytical Chemistry—Metallurgy—Reactor Radiations— Polymers— Inorganic Materials—Cry-
ogenics —Materials Evaluation Laboratory—
2
of Standard Reference Materials.
Office
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20234.
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3 Located at 5285 Port Royal Road, Springfield, Virginia, 22151.
UNITED STATES DEPARTMENT OF COMMERCE • John T. Connor, Secretary
NATIONAL BUREAU OF STANDARDS • A. V. Astin, Director
George T. Armstrong
Heat Division
Standards
Institute for Basic
National Bureau of Standards
Abstract 1
1. Introduction 1
7. Gas Imperfections of CH . 6
16. References 16
III
Calculation of the Heating Value of a Sample
of High Purity Methane for Use as a Reference Material
George T. Armstrong
Abstract
1. Introduction
(1) The energy unit in which the determination was made and
the unit to which it must be convert ed.
(2) The mass unit in which the determination was made and
the current accepted value of the mass unit.
(3) The temperature dependence of the heat of combustion.
(5) The current best value for the vapor pressure of water.
(6) The current best coefficients for the real gas behavior
of methane and its mixtures with small quantities of
H_0 and other impurities.
Note that the Btu as used in ASTM methods for gaseous fuels is
different from that used in ASTM methods for liquid petroleum fuels
and ASTM methods for coal and related solid fuels.
We interpret this as the International Practical Te^erature Scale
of 191+8, Text Revision of I960.
) ]
Table 1
Table 2
c 1 1
R (gas constant) = 8.31U3 ±0.0008 J (deg K)" mol' [2]
c 3 -1
V (ideal gas) = (2.21036 ±0.00010) x 10^ cm mol [2]
Table 3
1 1
C° (CH.) at 25°C = 8.439* cal deg" mol" [19]
P 4
3 -1 1
C° (0 ) at 25°C = 7.016 cal deg mol" [19]
2
a 1 1
C° (CO ) at 25°C = 8.87 cal deg" mol" [19]
p <.
1 1
C° (HO) at 15°C = 4.1858 Jg" (deg C)" [ul
P ^
1
H° -H° (H 0) = 20.8949 Jg" [U]
Q 5 2
1
H H (H 0) = 39.4962 Jg" [U]
25°C" 15.555°C 2
P(H 0) at 15°G = 0.017429 atm [5,6]
2
3 1
AH°[CH. (g)] at 25°C = 212.790 kcal mol" [Section 9]
C 4
t - 6o°f - 15 55555 °c
.
7
PV „ 1,015,913.01 x 28316.8U6592 x lo"
N
RT * (8.3m3 ±.0008) x 288.70555
3
1.198U52 ± .000115 mol ft"
The uncertainty in the number of moles per cubic foot is almost
solely due to the uncertainty of the gas constant R.
(Saturated Basis)
(1 - e) - (1 - 0.00026) = 0.9997U
This value for PV/RT is within the limits 0.99800 ±0.00005 suggested
by Jessup and so we retain the same uncertainty, but use our calculated
value of PV/RT for PV/RT (real, saturated) and also for PV/RT (real, dry).
1-177619 to.oooiiU
N (real, saturated) .99797 ±0.00005
»/ i j 1-198U52
N(real, dry)\ =
0>99797
= 1.200890 moles CHjAcubic foot real
gas) (dry basis).
. .
The enthalpy change in the ideal gas state at one atm pressure is
the same as the enthalpy change of the real gases at zero pressure The .
8
) )
1
AH? = -889.8UUO kJ mol" (1961)
(H°-^)(CH 1;
) = +5 x U.18U x 8.U39 - +176.5U39
AH^ = AH o
25 G
+ (H -H
T 25
)[C0
2
] + (l^-H^) [2BfeO(i )]
- (H^H^MCHjJ - (H -H ^)[20
T 2 2
]
For C02 (g), CH^(g), and 2 (g) we take Hj-H^ to be (T-25) x Cp at 25 °C and
calculate Ht-H2 £ for H2O from enthalpy tables. Values for Cp at 25°C are
selected from Wagman, et al. [19], as listed in Table 2. For water
we find enthalpy data by Osborne, Stimson, and Ginnings [lUl at one
atmosphere pressure, which has the values 10l4*899H J g at 25 °C
and 67.2632 J g" 1 at
>.
16 *C. Using an interpolated value of
Cp » U.l85lJg" deg" 1 for the heat capacity of water at 15.7777°C, we
calculate for the enthalpy difference Hi£°c " %5.5555°C = 1.86QO
J g -1 . The enthalpy difference H25°c-Kl5.^555°C = 39.U962 J g"
(that is 10U.899U - 67.2632 + 1+.1851 x .UUiUUl ) • This is equal to
-1
711.5375 J (mol) .
10
. ) ))
H H
l5.5555~ 25
J
C0 - 350.66
2
2^0(4) -1U23.09
20 + 55U.U8
2
CH, + 333-U7
AH° at 60°F
1
CI^(g,p=0) + 20 (g,p=0) =
2
2^000 + C0
2
(g,p=0) -891.196 kJ mol" (1 '
11
:
±0.08 J
9.
The value listed here differs slightly but not significantly from a
value informally reported previously. The difference is due to (a) a
slight change in heat capacities accepted for the reaction components,
and (b) a slight difference in the corrections to the molar heat of
reaction for non-ideality of gases at 30°C and at 15'5555°C.
12
13. Analysis of Two Special Methane Samples for Certification
Table 5
13
14.„ Heat of Combustion of the Two Special Samples
Only one heat of combustion was calculated for the two samples,,
It was calculated from equation (2), in which
A(U
c
)
c4
(sample) = AH (CH.) x An(CH.) + AH (C H,) x An(C_H A )
4 c <: o do
We take the uncertainty in the mole fraction of CH^, Aa(CH4), to be
the square root of the sum of the squares of the uncertainties in
the mole fractions of all the impurities. Since the major contribu-
tion to the uncertainty in CH4 is due to the uncertainty in C2H6,
An(C2H6) will be of opposite sign from An(CH4).
14
The combined uncertainty in heat of combustion of the sample
due to uncertainty in composition and uncertainty in heat of
combustion of methane is ^
(o. 3 6o)2 + (0.152)2
1
= ^„153 = 0.391 Btu (std cu ft)"
15
16„ References
[11] Fo Do Rossini, (a) J. Research Natl. Bur B Standards _6, 37-4-9 (1931).
(b) ibid. %, 329-30 (1931).
16
.
[16] A. E. Cameron and E. Wichers, J. Am. Chem. Soc, 84, 4-175-97 (1962).
[20] A. H. Cook, Phil. Trans. Roy. Soc. (London) 25U, 125-15U (1961-2).
17
FG , M NM-M*
(4-6-84)
APPENDIX Io
U.S. DEPARTMENT OF COMMERCE
NATIONAL BUREAU OF STANDARDS
WASHINGTON, D.C. 20234
of
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s
E.
^
Hughes, Chemist
y
(ohn K. Taylor, Chief
Analysis and Purification
Analytical Chemistry Division
65-423
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30- •o
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10-
^J
-f * t s
-* x 9"
T° K
Sources of Data
and C0 : NBS Circ. 564 [17]
2 2
CH . : H. E» Tester [18]
4
19
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