Fuel 200 (2017) 107112

Contents lists available at ScienceDirect

Fuel
journal homepage: www.elsevier.com/locate/fuel

Full Length Article

Capillary constant and surface tension of methane/hydrogen mixtures

V.G. Baidakov , A.M. Kaverin, K.A. Grishina
Institute of Thermal Physics, Ural Branch of the Russian Academy of Sciences, Amundsen St. 107a, Ekaterinburg 620016, Russia

h i g h l i g h t s g r a p h i c a l a b s t r a c t

The capillary constant of methane/

hydrogen mixtures has been
measured.

The surface tension of methane/
hydrogen mixtures has been
calculated.

The measurements were made by the
differential capillary method.

Equations for the capillary constant
and surface tension have been
offered.

Methane/hydrogen mixtures are a
promising kind of fuel for transport.

a r t i c l e i n f o a b s t r a c t

Article history: Methane/hydrogen mixtures are a promising kind of fuel for automobile, water and railway transport,
Received 15 February 2017 supersonic aircraft, and rocket engineering. We have used the differential capillary method to measure
Received in revised form 9 March 2017 the capillary constant a2 and calculate the surface tension r in the temperature range from 95 to
Accepted 13 March 2017
176 K and the pressure range from that of the saturated vapors of pure methane to 4 MPa. Equations have
been derived which describe the temperature, baric and concentration dependences of a2 and r. The
adsorption has been determined. The results of measurements are discussed in the framework of thermo-
Keywords:
dynamic models of the theory of surface phenomena.
Methane/hydrogen mixtures
Capillary constant
2017 Elsevier Ltd. All rights reserved.
Surface tension
Differential capillary method
Adsorption

1. Introduction Small additions of hydrogen to natural gas make it possible to

Natural gas, which mainly consists of methane, is an alternative
to products of petroleum refinement, namely, gasoline and diesel
fuel [13]. At present, this is the most economical, environmentally
clean and safe kind of fuel, which may be used in both compressed
and liquefied form. Liquefied natural gas is a promising fuel for
automobile, railway and water transport [4], supersonic aircraft
and rocket engineering [5]. As compared with traditional hydrocar-
bon kinds of fuels, methane has a lower normal rate of combustion.
Corresponding author.
E-mail address: baidakov@itp.uran.ru (V.G. Baidakov).
eliminate this disadvantage completely [6,7]. Enriched with hydro-
gen (up to 6 vol%), natural gas with a low content of methane (up
to 40 vol%) may be used as a fuel for gas-turbine electric genera-
tions [8]. Small amounts of hydrogen in gasoline or diesel fuel
are capable of saving up to 30% of the main fuel [9].
The use of hydrogen as an additional component of a standard
fuel requires reliable data on the properties of hydrogenous mix-
tures. The present paper shows the results of experimental inves-
tigations of the capillary constant and surface tension of
methane/hydrogen mixtures with a hydrogen content in the liquid
phase of methane up to 4.5 mol%.

http://dx.doi.org/10.1016/j.fuel.2017.03.043
0016-2361/ 2017 Elsevier Ltd. All rights reserved.
108 V.G. Baidakov et al. / Fuel 200 (2017) 107112
Surface tension plays a significant role at phase transitions
determining the tearing-off bubble size and the heat-transfer coef-
ficient during liquid boiling, the characteristic size of condensation
centers and the heat-transfer coefficient during drop wise conden-
sation. Under the action of capillary forces, a drop of a liquid jet
flowing out of a nozzle breaks up, and one can observe the devel-
opment of capillary waves at the free surface of the liquid.
2. Experiment
2.1. Materials
To prepare methane/hydrogen mixtures, use was made of
methane produced by the Moscow gas processing plant and hydro-
gen produced by UralCryoGas, Russia. The rated purity of methane
is 99.99%, and that of hydrogen, 99.999%. The main impurities in
methane were oxygen and nitrogen (no more than 0.006%) and
in hydrogen it was oxygen (no more than 0.0008%). The gases
did not undergo any additional purification.
2.2. Method
To determine the surface tension of methane/hydrogen mix-
tures, use was made of the differential capillary method [1012].
The measuring cell contained three glass capillaries. The internal
radii of the capillaries r were determined by calibration with
mercury and were as follows: r1 0:6393  0:0005 mm,
r2 0:2297  0:0003 mm, and r3 0:09607  0:00008 mm.
The cell was thermostatted (0.005 R) in an aluminum block, which
was mounted in the vacuum chamber of a cryostat. The temperature
in the block was measured by a platinum resistance thermometer
with an error that did not exceed 0.02 K. Before the beginning of
measurements, methane was condensed into the cell. The pressure
in the cell was measured by a spring-type pressure gauge. The accu-
racy of determination of the phase-equilibrium pressure was no
worse than 0.007 MPa. The methane/hydrogen mixture was pre-
pared right in the cell with liquefied methane by letting in hydrogen.
After the achievement of phase equilibrium, which was controlled
by the displacement of the menisci of a liquidgas interface, mea-
surements were made of the difference of the heights of liquid rise
in the capillaries hij . The values of hij obtained were used to calculate
the capillary constant
1 1
a2 hij =bi  bj ; 1 a4 1:180809.
where bi and bj are the radii of curvature of the menisci in the i-th
and j-th capillaries, which were determined with the supposition of
a complete wetting of the capillary walls by the liquid from the Lane
equation [13] by data on the capillary radii ri and r j .
A simultaneous use of three capillaries in an experiment made it
possible to obtain at a given temperature and pressure two indepen-
dent values of the capillary constant, which were averaged in the
course of processing. This increased the reliability of the data
obtained. The total relative error of determination of a2 at low tem-
peratures did not exceed 0.5% and reached (1.52.0)% at a temper-
ature of 176 K. The results of measuring a2 are presented in Table 1.
2.3. Calculations
The surface tension was calculated by the formula
1
r ga2 ql  qv : 2 pared with the results of some preceding papers [12,15,1722].
2
Here g 9:8162 m  s2 is the gravitational acceleration at the mea-
surement site, ql and qv are the liquid and vapor densities on the
phase-equilibrium line.
The values of ql and qv , and also the composition of the liquid
phase xl (the molar fraction of hydrogen) were determined by data
on the temperature and pressure of saturated vapors from the
equation of state for a methane/hydrogen mixture [14]. The results
of calculations are given in Table 1. Presented ibidem are the val-
ues of the surface tension.
3. Results and discussions
3.1. Approximations
In the whole range of state parameters investigated the capil-
lary constant of methane/hydrogen mixtures is a monotonically
decreasing function of pressure (Fig. 1) and concentration. A simi-
lar character of pressure and concentration (Fig. 2) dependence is
also observed for surface tension.
The pressure dependence z a2 or r is presented as follows:
z z Bp  p Dp  p 2 : 3
Here z a2 or r , and p p =pc are the capillary constant or sur-
face tension and the reduced pressure of saturated vapors of pure
methane, p p=pc , pc 4:598 MPa is the pressure at the critical
point of methane. The values of a2 , r , p , B and D are functions of
the temperature.
As shown in Refs. [10] and [15], temperature dependences of
the capillary constant and the surface tension of methane and
other cryogenic liquids in the whole temperature range from the
triple to the critical point within the experimental error may be
approximated by the equations
a2 a20 en ; 4
r r0 el 1 r1 e; 5
where e 1  T=T c , T c 190:54 K is the temperature at the critical
point of methane, a20 13:94 mm2 , n 0:906, r0 40:92 mN=m,
l 1:258, r1 0:095.
The pressure of saturated vapors of pure methane is adequately
described by an equation in the form suggested by Wagner [16]
ln p a1 e a2 e1:5 a3 e3 a4 e6 =1  e; 6
where a1 6:005918, a2 1:193242, a3 0:844288,
The forms of the functions BT and DT and the values of the
free parameters included in them have been determined by the
method of regressive analysis. Calculations have shown that both
for the capillary constant and for the surface tension the root-
mean-square deviation of experimental data from those calculated
by Eq. (3) is minimum if the functions BT and DT look like:
B b1 b2 e2 ; 7
D d1 d2 ee2 : 8
The values of the coefficients b1 , b2 , d1 and d2 for a and r are
2
given in Table 2. Fig. 3 shows the deviations of experimental values
of r from those calculated by Eq. (3). As is clear from Fig. 3, in the
whole temperature and pressure range investigated they are less
than 2%.
In Fig. 4 data on the surface tension of pure methane are com-
The best agreement is observed with the values of r obtained ear-
lier in our laboratory [12,15,17,18]. We do not known of any papers
on the measurement of the surface tension of methane/hydrogen
mixtures.
 V.G. Baidakov et al. / Fuel 200 (2017) 107112 109

Table 1
Temperature T, pressure p, capillary constant a2, hydrogen content in the liquid phase xl, densities of liquid ql and vapor qv phases, surface tension r of methane/hydrogen
mixtures.

T (K) p (MPa) a2 (mm2) xl (mol%) ql (kg/m3) qv (kg/m3) r (mN/m)

95 0.020 7.50 0 445.8 0.41 16.40
0.482 7.24 0.39 444.9 1.69 15.75
1.072 6.91 0.88 443.8 3.24 14.94
1.644 6.64 1.33 442.8 4.78 14.27
2.233 6.36 1.78 441.9 6.37 13.60
2.801 6.10 2.19 441.0 7.90 12.97
3.371 5.88 2.60 440.1 9.47 12.43
3.738 5.76 2.85 439.6 10.50 12.13
105 0.056 6.77 0 432.0 1.06 14.32
0.467 6.54 0.40 431.1 2.36 13.76
1.058 6.28 0.95 429.8 3.69 13.13
1.649 6.04 1.49 428.6 5.14 12.55
2.213 5.85 1.99 427.6 6.56 12.09
2.789 5.68 2.48 426.5 8.02 11.67
3.377 5.46 2.97 425.4 9.52 11.14
3.891 5.32 3.38 424.6 10.80 10.80
120 0.190 5.68 0 409.9 3.26 11.33
0.485 5.57 0.35 409.0 4.10 11.07
1.409 5.26 1.36 406.8 6.86 10.33
1.638 5.19 1.61 406.3 7.31 10.16
2.232 5.01 2.23 404.9 8.61 9.74
2.799 4.86 2.82 403.6 9.94 9.39
3.386 4.70 3.42 402.2 11.40 9.02
135 0.492 4.59 0 385.6 7.90 8.50
1.068 4.41 0.75 383.9 9.67 8.10
1.679 4.23 1.52 382.1 11.3 7.70
2.212 4.11 2.19 380.6 12.8 7.42
2.795 3.95 2.91 379.0 14.4 7.07
3.370 3.83 3.61 377.4 15.9 6.80
3.901 3.73 4.25 375.9 17.4 6.56
150 1.042 3.41 0 357.8 16.3 5.72
1.660 3.27 0.97 355.5 18.6 5.41
2.213 3.16 1.79 353.6 20.5 5.17
2.799 3.03 2.66 351.5 22.6 4.89
3.362 2.91 3.49 349.6 24.5 4.64
3.937 2.80 4.32 347.5 26.5 4.42
160 1.588 2.64 0 336.3 25.4 4.03
2.220 2.50 1.13 333.5 30.5 3.72
2.788 2.39 2.10 331.1 34.5 3.47
3.394 2.27 3.13 328.6 38.0 3.24
3.929 2.17 4.03 326.4 40.7 3.04
165 1.937 2.26 0 324.1 31.5 3.25
2.237 2.14 0.70 322.5 34.6 3.02
2.810 2.03 1.78 319.7 39.7 2.79
3.368 1.92 2.72 317.1 44.0 2.57
3.918 1.81 3.72 314.6 47.6 2.37
170 2.324 1.84 0 310.5 39.0 2.45
2.795 1.75 0.98 307.8 44.3 2.26
3.367 1.64 2.15 304.7 50.1 2.05
3.882 1.55 3.09 302.0 54.6 1.88
173 2.592 1.62 0 301.5 44.4 2.04
2.885 1.54 0.64 299.7 47.5 1.90
3.191 1.47 1.30 297.9 50.6 1.78
3.570 1.40 2.12 295.7 54.3 1.66
3.936 1.33 2.90 293.6 57.8 1.54
176 2.875 1.37 0 291.5 50.8 1.618
3.194 1.28 0.72 290.3 51.9 1.500
3.573 1.22 1.41 283.5 55.4 1.366
3.919 1.14 2.40 281.0 58.8 1.243

For the concentration dependence z a2 or r we may write an The smallest root-mean-square deviation of experimental data
equation similar to Eq. (3): from Eq. (9) is observed if the functions B0 and D0 are written as
follows:
z z B0 xl D0 x2l 9 B0 b1 b2 e b3 e2 e;
0 0 0
10

D0 d1 e3 :
0
Here the concentration xl is expressed in mol%. 11
110 V.G. Baidakov et al. / Fuel 200 (2017) 107112

Fig. 3. Deviations of experimental values of surface tension rexp from those

calculated by Eq. (3) 1 T = 95; 2 105; 3 120; 4 135; 5 150; 6 160; 7 165;
8 170; 9 173; 10 176 K.

Fig. 1. Capillary constant of methane/hydrogen mixtures as a function of pressure

along isotherms: 1 T = 95; 2 105; 3 120; 4 135; 5 150; 6 160; 7 165;
8 170; 9 173; 10 176 K. A dashed line shows the capillary constant of pure
methane, solid lines, Eq. (3).

Fig. 4. Deviations of experimental values of surface tension rexp of pure methane

from those calculated by Eq. (5): 1 the present paper; 2 Baidakov, Khvostov,
Muratov [15], 3 Baidakov et al. [12], 4 Baidakov, Grishina [17], 5 Baidakov,
Kaverin, Khotienkova [18], 6 Blagoi et al. [19], 7 Fuks, Bellemans [20], 8 Sprow,
Prausnitz [21], 9 Blagoi [22].

on the pressure and the phase composition. According to the finite

thickness layer method [23]

 
dr xr  xl
Fig. 2. Surface tension of methane/hydrogen mixtures as a function of hydrogen s tr  tl  tv  tl ; 12
concentration along isotherms: 1 T = 95; 2 105; 3 120; 4 135; 5 150; dp T xv  xl
6 160; 7 165; 8 170; 9 173; 10 176 K. Solid lines show Eq. (9).
where s is the surface per mole of the surface layer, tl , tv and tr are
the molar volumes of the liquid and vapor phases, and the surface
0 0 0 0
layer, xl , xv and xr are the molar fractions of hydrogen in the liquid
The values of the coefficients b1 , b2 , b3 and d1 are given in and vapor phases, and the surface layer.
Table 2. The pressure dependence of surface tension is connected with
the redistribution of components between the coexistent phases
3.2. Thermodynamic description and the surface layer. This mechanism shows up most vividly in
the critical region, which leads to an essential difference of pres-
Let us consider thermodynamic relations that describe the sure dependences of surface tension close to and away from the
isothermal dependence of the surface tension in a binary system critical point.

Table 2
Coefficients of Eqs. (7), (8) and (10), (11).
0 0
bi, di Eqs. (7) and (8) b i , di Eqs. (10) and (11)
a2 (mm2) r (mN/m) a2 (mm2) r (mN/m)
0
b1 0.869712 1.557154 b1 1.4055710 2.6090850
0
b2 6.415870 19.165170 b2 5.2648250 9.6039170
0
d1 9.504567 19.791230 b3 10.1595100 22.0950000
0
d2 15.330830 28.147320 d1 0.1937314 0.5938643
 V.G. Baidakov et al. / Fuel 200 (2017) 107112 111

If the liquid and the vapor are far from the critical state
(tv  tl ), and the composition of the surface layer is intermediate
between the compositions of the coexistent phases (xv > xr > xl ),
then from Eq. (12) follows
 
dr xr  xl
s  tv : 13
dp T xv  xl
The sign of the derivative dr=dpT is determined by the sign of
the concentration factor, which in the approximation adopted is
always positive, and the surface tension decreases with increasing
pressure.
If the content of the gas component (hydrogen) in the surface
layer exceeds considerably its content in the liquid phase
(xr >> xl ), then Eq. (12) takes the form
 
dr xr
s  tv  tl : 14
dp T xv  xl
Since the value of tv  tl is positive, from (14) it also follows that
with an increase in the pressure the surface tension must decrease. Fig. 5. Isotherms of relative adsorption in a methane/nitrogen system: 1 T = 95;
At the approach to the critical point tr  tl ! 0, xr  xl ! 0, 2 105; 3 120; 4 135; 5 150; 6 170 K.

tl ! tv , and tv  tl =xv  xl ! dt=dxc . The derivative

dt=dxc , which determines the shape of the curve of coexistence
of phases close to the critical point, is finite, therefore from the The results of calculating adsorption isotherms in a methane/
conditions written and Eq. (12) it follows that at the critical point hydrogen system by Eq. (18) with the use of data obtained for
dr=dpT;c 0, i.e. at the approach to the critical point the slope of surface tension are presented in Fig. 5.
If the molar surface of a solution is an additive function of the
the surface tension isotherm decreases, which is confirmed by the
composition, then the molar fraction of one of the components in
experimental data obtained.
the surface layer and the relative adsorption are related by the fol-
Assuming that the thickness of the surface layer does not
lowing equation [23]
change with changes in its composition, and the relationship
between the values of xr and xl is linear, i.e. xr k xl , for the iso- xl s C21 1  xl
therm of an ideal binary mixture far from the critical state one xr  : 19
1  s  s C21 1  xl
can write [23]
RT1  k 1 1 c  1k xl This equation makes it possible to check the consistency of two
r r ln : 15 approaches to the description of the surface layers of binary mix-
s 1 c  1k 1  xl
tures the methods of finite thickness layer and interfaces and
where R is the universal gas constant, c s =s , s and s are the to evaluate the effective thickness of the interface. According to
molar surfaces of pure methane and hydrogen. (19), the proportionality coefficient k in the initial segment of the
At xl
1 Eq. (15) is rearranged to give (9), that is isotherm of the surface layer composition is equal to 20.19, which
is in good agreement with its calculation from Eq. (16) (k = 20.57)
RT1  k RT1  k1 c  1k 2
r r xl  xl : 16 and points to the fact that at T 95 K the minimum possible thick-
s 2s
ness of the surface layer is close to one monolayer.
The molar surface of a pure solvent (methane) s may be calcu-
lated by the formula
4. Conclusion
tl 2=3 N 1=3
s A
; 17
i The differential method of capillary rise has been used to mea-
where tl is the molar volume of pure methane in the liquid phase, sure the capillary constant and calculate the surface tension of
N A is the Avogadro number, and i is the number of monolayers in methane/hydrogen mixtures. Experiments were conducted in a
the surface layer. wide temperature range at pressures up to 4 MPa. It has been
found that small additions of hydrogen into methane reduce its
From Eq. (17) for pure methane at T 95 K and i 1 we have
surface tension. The latter is connected with the fact that hydrogen
s 9:20  104 m2 =mol. Formulas (9) and (16) make it possible
in methane is a surface-active substance and is adsorbed at a liq-
now to determine the value of the proportionality coefficient for
uidvapor interface. The data obtained on a2 and r, as functions
the isotherm of the composition of the surface layer k and the value
of the temperature, pressure and concentration, are described by
of the parameter c, connected with the dimensions of the mole-
analytical dependences. The results of experimental investigations
cules of the solvent and the substance being dissolved. At
of the properties of a liquidvapor interface in a methane/hydro-
T 95 K we have k 20:57 and c 0:518. The fact, that k > 1
gen system are in agreement with the data of molecular dynamics
and c < 1 means that in a two-phase methane/hydrogen system
simulation [25,26].
one can observe positive adsorption, the substance with smaller
molecules (hydrogen) acting as a surface active one.
The relation between surface tension and relative adsorption Acknowledgements
C21 is established by the well-known Gibbs equation [24], which
for a weak solution takes the form The work has been supported by the Russian Foundation for
  Basic Research (grant N 15-08-03399) and the Complex
xl 1  xl dr
C21  18 Programme of Fundamental Investigations of the Ural Branch of
RT dxl T the Russian Academy of Sciences (grant N 15-1-2-6).
112 V.G. Baidakov et al. / Fuel 200 (2017) 107112

References [14] Kunz O, Klimeck R, Wagner W, Jaeschke M. The GERG-2004 wide-range

equation of state for natural gases and other mixtures. GERG Technical
Monograph 15. VDI Verlad CmbH, Dsseldorf; 2007.
[1] Semin, Bakar RA, Ismail AR. Green engines development using compressed
[15] Baidakov VG, Khvostov KV, Muratov GN. Surface tension of nitrogen, oxygen
natural gas as an alternative fuel: a review. Am J Environ Sci 2009;5
and methane in a wide temperature range. Zhurnal Fiz Khim 1982;56
(3):37181.
(4):8147.
[2] Turrio-Baldassari L, Battistelli CL, Conti L, De Berardis B, Iamiceli AL, Gambino
[16] Baidakov VG. Thermophysical properties of superheated liquids. Sov Tech Rev
M, et al. Evaluation of emission toxicity of urban bus engines: compressed
B 1994;5:188.
natural gas and comparison with liquid fuels. Sci Total Environ
[17] Baidakov VG, Grishina KA. Capillary constant and surface tension of methane
2006;355:6477.
helium solution. Fluid Phase Equilib 2013;354:2459.
[3] Munde GG, Dalu RS. Compressed natural gas as an alternative fuel for spark
[18] Baidakov VG, Kaverin AM, Khotienkova MN. Surface tension of ethane
ignition engine: a review. Int J Eng Innovative Technol 2012;2(6):926.
methane solutions: 1. Experiment and thermodynamic analysis of the results.
[4] Wegrzyn J, Gurevich M. Liquefied natural gas for trucks and buses. SAE
Fluid Phase Equilib 2013;56:905.
Technical Paper Series 2000;2000-01-2210:16.
[19] Blagoi YP, Kireev VA, Lobko MP, Pashkov VV. Surface tension of krypton,
[5] Contreras A, Yiit S, zay K, Vezirolu TN. Hydrogen as aviation fuel: a
methane, deuteromethane and oxygen. Ukr Fiz Zhurnal 1970;5(3):42732.
comparison with hydrocarbon fuels. Int J Hydrogen Energy 1997;22(10
[20] Fuks S, Bellemans A. The surface tension of krypton, methane and their
11):105360.
mixture. Physica 1966;32(3):594602.
[6] Karim GA, Wierzba I, Al-Alousi Y. Methane-hydrogen mixtures as fuels. Int J
[21] Sprow FB, Prausnitz JM. Surface tensions of simple liquids. Trans Faraday Soc
Hydrogen Energy 1996;21(7):62531.
1966;62:1097104.
[7] Huang Z, Wang J, Liu B, et al. Combustion characteristics of a direct-injection
[22] Blagoi YP. Surface tension of solutions of liquefied gases N2Ar, N2CH4, Ar
engine fueled with natural gashydrogen blends under different ignition
CH4. Ukr Fiz Zhurnal 1960;5(1):10914.
timings. Fuel 2007;86(3):3817.
[23] Rusanov AI. Phasengleichgewichte und Grenzflachenerscheinungen. Berlin:
[8] Collantes G, Melaina MW. The co-evolution of alternative fuel infrastructure
Akademie-Verlag; 1978.
and vehicles: a study of the experience of Argentina with compressed natural
[24] Gibbs J.W. The Collected Works of J. Willard Gibbs. Thermodynamics.
gas. Energy Policy 2011;39(2):66475.
Longmans, Green and Co.: New York; 1928 [vol. 1].
[9] Tseng C. Effects of hydrogen addition on methane combustion in a porous
[25] Protsenko SP, Baidakov VG. Binary Lennard-Jones mixtures with highly
medium burner. Int J Hydrogen Energy 2002;27(6):699707.
asymmetric interactions of the components. 1. Effect of the energy
[10] Baidakov VG. Interface of simple classical and quantum
parameters on phase equilibria and properties of liquidgas interfaces. Fluid
liquids. Ekaterinburg: Nauka; 1994.
Phase Equilib 2016;429:24253.
[11] Baidakov VG, Sulla II. Surface tension in heliumoxygen and heliumethane
[26] Protsenko SP, Baidakov VG, Bryukhanov VM. Binary Lennard-Jones mixtures
solutions. Int J Thermophys 1995;16(4):90927.
with highly asymmetric interactions of the components. 2. Effect of the
[12] Baidakov VG, Khotienkova MN, Andbaeva VN, Kaverin AM. Capillary constant
particle size on phase equilibria and properties of liquidgas interfaces. Fluid
and surface tension of methanenitrogen solutions: 1. Experiment. Fluid Phase
Phase Equilib 2016;430:6774.
Equilib 2011;301(1):6772.
[13] Lane JE. Correction terms for calculating surface tension from capillary rise. J
Coll Int Sci 1973;42(1):1459.