Heat Transfer

Understand
Temperature Change in
Process Stream Mixing
Dharmendra Tiwary The isobaric and adiabatic mixing of
Hyprotech Ltd., non-reactive process streams can yield
Aspen Technology, Inc.
Anil K. Mehrotra
an outlet stream temperature that is either
Univ. of Calgary between, higher than, or lower than
the inlet stream temperatures.
This article uses process simulation software
to explore temperature-change scenarios
in the mixing of normal alkanes.

C
onsider the mixing of a hot process stream A, hav- specified process conditions, along with mass and energy
ing a temperature TA and at pressure P, with a cold balances. In other words, the equilibrium mixed-stream
process stream B, having a temperature TB and at temperature depends on the type of species, composition,
pressure P (Figure 1). The non-reactive mixing, with neg- temperature, pressure, phase (or state), non-ideal behavior,
ligible heat of solution, is accomplished under isobaric and and the relative amounts of the process streams being
adiabatic conditions, i.e., the pressure of the mixture mixed. In this regard, the latent heat of phase transforma-
remains at P and there is no heat lost to or gained from the tion and/or the heat of mixing of the process streams plays
surroundings. Will the equilibrium temperature of the a significant role in determining whether (TA TC TB),
mixed stream C, TC, be: (TC > TA, TB) or (TC < TA, TB).
a. higher than TA Through a set of illustrative calculations, this article
b. lower than TB demonstrates that the correct answer to the above question
c. somewhere between TA and TB is: d any of the above. It presents a comprehensive set
d. any of the above?
A common notion regarding this type of mixing
shared by many process engineers as well as chemical engi-
neering students is that the mixed-stream temperature Stream A
will always be between those of the individual process @ TA , P Mixer
streams, i.e., TA TC TB. However, this is not necessarily Isobaric, Stream C
Adiabatic @ TC , P
true. Even without any endothermic or exothermic chemical and
Stream B Non-reactive
reaction and negligible heat of solution, TC could be @ TB , P
between (TA TC TB), higher than (TC > TA, TB) or lower Q=0
than (TC < TA, TB) the temperatures of the inlet streams.
The mixed-stream temperature, TC, depends on phase
equilibria considerations, i.e., the relative distribution of
Figure 1. Isobaric, adiabatic, non-reactive mixing of two
components in different phases under equilibrium at the process streams.

CEP September 2006 www.aiche.org/CEP 33

Heat Transfer

of results (obtained using the HYSYS process simulation
software) to evaluate the change in temperature during adia-
batic and isobaric mixing of process streams in non-reactive
systems. The process streams are pure n-alkanes, ranging
from methane (CH4, denoted by C1) to n-dodecane (C12H26,
denoted by C12), which are non-reactive over the tempera-
ture and pressure conditions considered here. Binary mix-
tures of n-alkanes are studied in order to keep the calcula-
tions simple; however, the principle can be extended to
more complex multicomponent mixtures.
The predicted values of selected properties of the n-
alkanes are listed in the table. Note that at P = 1 atm
(101.3 kPa) and over the temperature range of 0100C,
C1 exists as a gas, C2 to C4 exist as a vapor, C5 to C7 as a
liquid or vapor, and C8 to C12 as a liquid.
Calculating the change in temperature
Before looking at the simulation results, it is useful to
review the underlying calculations for the change in tem-
perature resulting from adiabatic and isobaric mixing of
two process streams. Several simplifying assumptions are
made here; for more accurate and rigorous techniques,
the reader should consult textbooks on chemical engi-
neering thermodynamics and mass and energy balances,
such as Refs. 16.
Assume that mA kg of stream A, which exists as vapor
at TA and P, is mixed with mB kg of stream B, which
exists as liquid at TB and P, resulting in an outlet stream
C, consisting of vapor and/or liquid phases. To simplify
the mathematical representation, both inlet streams are
considered to be at the same temperature, Tin (= TA = TB).
While the pressure is held at P during the isobaric mixing
of streams A and B, the temperature of the outlet mixed
stream C, of mass mC (= mA + mB), is denoted by Tout (=
TC). For adiabatic mixing (i.e., Q = 0) with negligible heat
of mixing, the total enthalpy of the outlet stream is equal
to the sum of the enthalpies of the inlet streams; hence, the
total enthalpy of the outlet mixture, mCHC, is mAHA +
mBHB, where HA and HB are the mass enthalpies (in J/kg),
at Tin and P, of streams A and B, respectively.
Assume that at equilibrium, fA mass fraction of vapor A
condenses and/or fB mass fraction of liquid B vaporizes. The

Table. Selected thermal properties of n-alkanes ranging from CH4 to C12H26 predicted by HYSYS.

Properties at 1 atm Properties at 20C

Normal Latent Latent
Boiling Heat of Vapor Heat of Specific Heat Capacity at 1 atm, kJ/kg-C
Point, Vaporization, Pressure, Vaporization, (Blue values are for liquid phase)
Alkane C kJ/kg kPa kJ/kg 0C 20C 40C 60C 80C 100C

CH4 161.5 512.2 NA* NA* 2.20 2.24 2.28 2.34 2.39 2.45
(C1, methane)
C2H6 88.6 487.5 3,787.5 192.0 1.68 1.75 1.82 1.90 1.98 2.06
(C2, ethane)
C3H8 42.1 424.2 836.1 347.0 1.60 1.69 1.77 1.86 1.94 2.02
(C3, propane)
C4H10 0.5 386.3 206.5 368.9 1.58 1.68 1.77 1.86 1.95 2.04
(C4, n-butane)
C5H12 36.1 358.9 56.34 370.2 2.12 2.24 1.76 1.85 1.94 2.03
(C5, n-pentane)
C6H14 68.7 336.5 16.25 366.1 2.04 2.15 2.26 2.37 1.92 2.01
(C6, n-hexane)
C7H16 98.4 318.4 4.89 361.6 2.00 2.10 2.21 2.31 2.42 2.01
(C7, n-heptane)
C8H18 125.7 304.2 1.47 359.0 1.98 2.09 2.19 2.29 2.40 2.50
(C8, n-octane)
C9H20 150.8 290.7 0.46 354.7 1.98 2.07 2.17 2.26 2.36 2.45
(C9, n-nonane)
C10H22 174.2 278.6 0.15 350.7 1.96 2.05 2.15 2.24 2.33 2.42
(C10, n-decane)
C11H24 195.9 269.7 0.05 350.0 1.96 2.05 2.14 2.23 2.32 2.41
(C11, n-undecane)
C12H26 216.3 258.2 0.02 343.4 1.94 2.03 2.12 2.21 2.30 2.39
(C12, n-dodecane)

* Not applicable, because CH4 (gas) at 20C is above its critical temperature of 82.8C

34 www.aiche.org/CEP September 2006 CEP

 10
Nomenclature
A = inlet stream A (vapor)
0
B = inlet stream B (liquid) C10

Temperature Change, T, C
C9
C = outlet mixed-stream C
C8
Cn = n-alkane (CnH2n+2) 10
CpL = average specific heat capacity of liquid phase, J/kg-C
C7
CpV = average specific heat capacity of vapor phase, J/kg-C
fA = mass fraction of A condensed into the liquid phase 20
fB = mass fraction of B vaporized into the vapor phase C6
H = mass enthalpy, J/kg 30
HA = mass enthalpy of stream A, J/kg
HB = mass enthalpy of stream B, J/kg
HC = mass enthalpy of mixed-stream C, J/kg 40 C5
HV = latent heat of vaporization, J/kg

(Hv)A = latent heat of vaporization of A at Tin, J/kg
(Hv)B = latent heat of vaporization of B at Tin, J/kg
mA = mass of stream A, kg
mB = mass of stream B, kg
mC = mass of mixed-stream C (= mA + mB), kg
P = pressure, Pa or atm
PV = vapor pressure, Pa
Q = heat lost to or absorbed from surroundings, J
T = temperature, C
TA = temperature of inlet stream A, C
TB = temperature of inlet stream B, C
TC = temperature of mixed-stream C, C
Tin = inlet-stream temperature (= TA = TB), C
Tout = outlet-stream temperature (= TC), C
T = change in temperature (= Tout Tin),C
numerical values of fA and fB can be determined from vapor-
liquid equilibrium flash calculations. Using (HV)A and
(HV)B to denote the latent heat of vaporization (in J/kg) of A
and B at Tin, the energy released by fAmA kg of vapor A is
fAmA(HV)A and the energy absorbed by fBmB kg of liquid B
is fBmB(HV)B. Therefore, the net amount of energy released
(or absorbed) is equal to fAmA(HV)A fBmB(HV)B. This
released (or absorbed) energy determines the magnitude of
increase (or decrease) in the outlet temperature, Tout.
The average specific heat capacities (in J/kg-C) of the liq-
uid and vapor phases are denoted by CpL and CpV, respective-
ly. The change (increase or decrease) in temperature, T, as a
result of mixing streams A and B is given by Eq. 1 below.
Obtaining T from Eq. 1 involves iterative calculations,
because Tout, as well as CpV and CpL, are needed for esti-
mating fA and fB. The sign of T depends on the relative
magnitudes of fBmB(HV)B and fAmA(HV)A.

Equation 1 for calculating temperature change.
50
0.0 0.2 0.4 0.6 0.8 1.0
Mass Fraction of CH4

Figure 2. Decrease in temperature for adiabatic mixing of
methane (CH4) with n-alkanes (C2H6 to C12H26).
Note that the phases actually present in the outlet
stream also depend on the relative amounts of A and B, mA
and mB. For example, when mA >> mB, the outlet stream
would most likely be a single-phase vapor stream, and
vice versa. Moreover, for the mixing of n-alkanes consid-
ered here, if both inlet streams were either liquid or vapor,
the outlet stream would also be liquid or vapor, respective-
ly. This generalization about phases, however, may not be
valid for some systems, such as eutectic mixtures.
Simulation results
Sample results for the temperature change due to mixing
are presented for: the C1+Cn mixtures at 20C and 1 atm;
the Cn+C12 mixtures at 20C and 1 atm; the C1+C8 mixture
at 0100C at 1 atm; the C3+C12 mixture at 0100C and 1
atm; and the C1+Cn mixtures at 20C and at two pressures,
5 and 10 atm. All numerical results were obtained from
HYSYS using the PengRobinson (7) equation of state.
Effect of composition:
Adding CH4 to C2 through C12
Figure 2 presents the predictions for the change in temper-
ature when C1 (stream A) at 20C and 1 atm is mixed individ-
ually with each of C2 to C12 (stream B), also at 20C and 1
atm. The temperature of every mixture, from C1+C2
to C1+C12, decreases at all concentrations of C1.
For C1+C2, C1+C3 and C1+C4 mixtures, the
decrease in temperature is small, since C2, C3 and
C4 are gas or vapor at 20C and 1 atm. For these
gas-phase mixtures, the predicted decrease in tem-

CEP September 2006 www.aiche.org/CEP 35

Heat Transfer
20
15
Temperature Change, T, C
10
5 80C
0 100C
5 0.0
0.0 0.2 0.4
Mass Fraction of C12

Figure 3. Increase in temperature for adiabatic mixing of
n-dodecane (C12H26) with n-alkanes (CH4 to C11H24).
perature is less than 0.4C, which is attributed to non-ide-
alities, e.g., the effect of the heat of mixing.
There is a substantial temperature decrease when C1 is
mixed with C5 and heavier n-alkanes. The largest tem-
perature decrease is for C1+C5 mixtures, but its magni-
tude becomes smaller for mixtures with the heavier n-
alkanes, due to their lower vapor pressures (PV) at 20C.
Each of the curves in Figure 2 has a minimum, which
shifts to the right (toward the higher mass fractions of
C1) with an increase in the carbon number of the n-alka-
nes. The maximum temperature decrease becomes small-
er with an increase in the carbon number due to lower
PV. The decrease in temperature for C1+C11 and C1+C12
mixtures is predicted to be less than 1C for all concen-
trations of C1.
A decrease in temperature (i.e., a negative T in Eq. 1)
upon mixing of C1 with C5+ implies fBmB(HV)B >
fAmA(HV)A. Since C5 to C12 exist as liquids at 20C and 1
atm, the mixing of C1 with C512 causes their vaporization,
which results in a high value of fB for the C1+C5 to C1+C10
mixtures. Since fB is directly related to the vapor pressure,
the small temperature changes for the C1+C11 and C1+C12
mixtures are attributed to the relatively low vapor pres-
sures of C11 and C12 at 20C.
Effect of composition:
Adding C12 to C1 through C11
The predictions in Figure 3 represent the change in
temperature when C12 is mixed individually with each of
C1 to C11 at 20C and 1 atm. Since pure C12 exists as
36 www.aiche.org/CEP September 2006
0
0C
C4
20C
Temperature Change, T, C
10
40C
20
60C
30
C3
C2 40
50
0.2 0.4 0.6 0.8 1.0
0.6 0.8 1.0
Mass Fraction of CH4

Figure 4. Effect of inlet-stream temperature on temperature
change for mixing of methane (CH4) with n-octane (C8H18).
liquid at these conditions (with a very low vapor pres-
sure of 0.02 kPa), it is labeled as stream B and C2 to C12
as stream A.
There is an increase in temperature only for the
C2+C12, C3+C12 and C4+C12 mixtures at all concentrations
of C12. For all other C12+alkane mixtures, the change in
temperature is much smaller and is negative, which is
attributed to the effects of non-ideality. For example, the
decrease in temperature for the C1+C12 gas-liquid mixture
is less than 0.5C. Likewise, the mixing of C12 with C5+
caused a small decrease in temperature, which was less
than 1C for the C5+C12 and C6+C12 mixtures and less
than 0.5C for the C7+C12 to C11+C12 mixtures.
For the C2+C12, C3+C12 and C4+C12 mixtures, the tem-
perature-change trends in Figure 3 are opposite those in
Figure 2. The temperature increase is largest for the
C4+C12 mixture, and its magnitude becomes smaller for
C2+C12 and C3+C12 mixtures, which can be attributed to a
lower solubility of C2 and C3 in C12 at these conditions.
The curves for the C2+C12, C3+C12 and C4+C12 mixtures
in Figure 3 have a maximum, which shifts to the right
(toward higher mass fractions of C12) as the carbon num-
ber of the lighter constituents decreases.
An increase in temperature (i.e., a positive T in Eq. 1)
upon mixing of C12 with C2, C3 and C4 means that
fAmA(HV)A > fBmB(HV)B. Since C2, C3 and C4 exist as
vapor at 20C and 1 atm, they are condensed into the rela-
tively non-volatile C12, which yields a relatively higher
value of fA along with a lower value of fB for C2+C12,
C3+C12 and C4+C12 mixtures.
CEP
 10 10

0
0C
C8
Temperature Change, T, C

C7
5 20C 10
C6
40C
20
C5
0
60C 30

80C 40 C4

Temperature Change, T, C
5
100C 50 (a) 5 atm

60

10
0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0
10
Mass Fraction of C3

0

Figure 5. Effect of inlet-stream temperature on temperature C7
change for mixing of propane (C3H8) with n-dodecane (C12H26). C6
10

20 C5
Effect of temperature (0100C)
Consider next the effect of inlet-stream temperature,
Tin, on the change in temperature, T, at P = 1 atm. 30
C4
The results for two mixtures, C1+C8 and C3+C12, at
40
0100C are presented in Figures 4 and 5, respectively.
As noted previously, at 20C and 1 atm, mixing C1
50 (b) 10 atm
with C8 gives a negative T, whereas mixing C3 with C3
C12 gives a positive T.

In Figure 4, for the C1+C8 mixture, as Tin increases,
the magnitude of T also increases. An increase in Tin
implies a lower solubility of C1 in C8, as well as an
increased vapor pressure of C8. That is, the magnitude
of fAmA(HV)A in Eq. 1 decreases with an increase in
Tin, while that of fBmB(HV)B increases. The combina-
tion of these two effects leads to a decrease in tempera-
ture upon mixing.
The results for the C3+C12 mixture shown in Figure 5
reveal very interesting trends. The C3+C12 mixture has a
negative T at the lower Tin of 020C for all composi-
tions, with the largest change occurring at the lowest Tin of
0C. However, the predictions at the higher Tin of
40100C show two peaks: a minimum and a maximum.
At these higher Tin values, T is positive for C12-rich mix-
tures but negative for C3-rich mixtures. At the highest Tin
of 100C, the magnitude of T for the C3-rich mixtures is
much larger than that for the C12-rich mixtures.
The behavior at the higher Tin of 40100C can be
explained as follows. For consistency, C3 (vapor) is
denoted as stream A and C12 (liquid) as stream B. For
the C12-rich mixtures, all or nearly all of the C3 added
60
0.0 0.2 0.4 0.6 0.8 1.0
Mass Fraction of CH4

Figure 6. Effect of pressure on temperature change for mixing
of methane (CH4) with n-alkanes (C2H6 to C12H26).
as vapor condenses into the C12-rich liquid phase, with
a high value of fA. This results in fAmA(HV)A >
fBmB(HV)B, which corresponds to a positive T in Eq.
1. For the C3-rich mixtures, on the other hand, a signif-
icant fraction of C12, fB, vaporizes due its increased
vapor pressure at higher temperatures, such that
fBmB(HV)B > fAmA(HV)A; hence, T is negative.
Effect of pressure (110 atm)
Figure 6 illustrates the effect of pressure on T for
C1+Cn mixtures at a constant Tin of 20C, at two pres-
sures, 5 atm (507 kPa) and 10 atm (1,013 kPa). These
results can be compared with the results for the C1+Cn
mixtures at P = 1 atm in Figure 2, which show a temper-
ature decrease for the mixtures of C1 and C5C10. As
shown in the table, at 20C and 1 atm, C1 exists as gas,

CEP September 2006 www.aiche.org/CEP 37

Heat Transfer
C2 to C4 as vapors, and C5 to C12 as liquids. As men-
tioned previously, at 20C and 1 atm, the C1+C2, C1+C3
and C1+C4 mixtures as well as the C1+C11 and C1+C12
mixtures did not give rise to any significant change in
temperature. Figure 2 also shows that the largest T at 1
atm is for the C1+C5 mixture, followed by the C1+C6
mixture, and so on.
At 20C and 5 atm (Figure 6a), the largest T is for
the C1+C4 mixture, followed by the C1+C5 mixture,
and so on. Note that, in Figure 2, the C1+C4 mixture
did not experience a significant change in temperature
at 1 atm. The difference in behavior is attributed to C 4
undergoing a phase transformation from vapor at 1 atm
to liquid at 5 atm. Compared with the results in Figure
2, the magnitudes of the temperature changes for the
C1C5+ mixtures at 5 atm are smaller than those at 1
atm. This is attributed to changes in both fA and fB, as
well as a decrease in HV when the pressure is
increased from 1 atm to 5 atm.
At 20C and 10 atm (Figure 6b), the largest T is for
the C1+C3 mixture, followed by the C1+C4 mixture, and so
on. Once again, the C1+C2 mixture did not have any sig-
nificant change in temperature, which is similar to the
results at 1 atm (Figure 2) and 5 atm (Figure 6a).
However, C3 undergoes a phase transformation at 20C
from vapor at 5 atm to liquid at 10 atm. The magnitudes
of T for all C1C412 mixtures at 10 atm (Figure 6b) are
smaller than those at 5 atm, which is again attributed to
changes in both fA and fB, as well as a decrease in HV due
to an increase in pressure from 5 atm to 10 atm.
Literature Cited
1. Felder, R. M., and R. W. Rousseau, Elementary
Principles of Chemical Processes, 3rd ed., John Wiley,
Hoboken, NJ (2000).
2. Poling, B. E., et al., The Properties of Gases and
Liquids, 5th ed., McGraw-Hill, New York, NY (2000).
3. Reid, R. C., et al., The Properties of Gases and
Liquids, 4th ed., McGraw-Hill, New York, NY (1987).
4. Sandler, S. I., Chemical and Engineering
Thermodynamics, 3rd ed., John Wiley, Hoboken, NJ
(1998).
5. Smith, J. M., et al., Introduction to Chemical
Engineering Thermodynamics, 6th ed., McGraw-Hill,
New York, NY (2000).
6. Walas, S. M., Phase Equilibria in Chemical
Engineering, ButterworthHeinemann (Elsevier),
Burlington, MA (1985).
7. Peng, D.-Y., and D. B. Robinson, A Two Constant
Equation of State, Industrial & Engineering Chemistry
Fundamentals, 15 (1), pp. 5964 (1976).
38 www.aiche.org/CEP September 2006 CEP
Concluding remarks
Computer simulations for the mixing of two non-
reacting n-alkane streams under isobaric and adiabatic
conditions demonstrate that the outlet-stream equilibri-
um temperature could be higher than, lower than, or
about the same as the inlet-stream temperature(s). That
is, the equilibrium mixture temperature does not
always have to be between the temperatures of the
individual streams.
For non-reactive systems without significant heat of
mixing, the temperature change during the mixing process
can be neglected, as long as there is no phase transforma-
tion. However, even for non-reactive systems, the temper-
ature change can be significant when the components
undergo phase transformation during the mixing process.
Among the parameters affecting the temperature increase
or decrease are the inlet temperature and pressure of the
process streams, as well as their compositions, vapor pres-
sures, enthalpies, latent heats of vaporization, specific heat
capacities, etc.
Although the cases examined in this article deal only with
vapor-liquid phase transformations, similar temperature
changes could also be encountered in the mixing of liquid
and solid streams (i.e., in melting or freezing) and vapor and
solid streams (i.e., in sublimation or desublimation). CEP
DHARMENDRA TIWARY is currently a process engineer with Canadian
Natural Resources Ltd (CNRL, Suite 1800, 324 8 Avenue SW, Calgary,
AB, Canada, T2P 2Z2; E-mail: dharmendra.tiwary@cnrl.com). Prior to
joining CNRL, he was a senior staff consultant with Aspentech
(Calgary, AB) and a process engineer in a petroleum refinery of Indian
Oil Corporation Ltd (Panipat, India). He is a registered professional
engineer with the Association of Professional Engineers, Geologists &
Geophysicists of Alberta (APEGGA) and a member of AIChE. He
received a bachelors degree in chemical engineering from Indian
Institute of Technology (IIT, Kharagpur, India) and a masters degree in
chemical engineering from the Univ. of Calgary.
ANIL K. MEHROTRA is a professor of chemical engineering and director of
the Centre for Environmental Engineering Research and Education
(CEERE) in the Schulich School of Engineering at the Univ. of Calgary
(2500 University Drive NW, Calgary, AB, Canada, T2N 1N4; E-mail:
mehrotra@ucalgary.ca). His research interests include transport and
thermophysical properties of bitumens and paraffinic heavy crude
oils, kinetics of wax deposition, and soil remediation. He is a
registered professional engineer with the Association of Professional
Engineers, Geologists & Geophysicists of Alberta (APEGGA), a fellow
of the Chemical Institute of Canada (CIC), and a member of the
Canadian Society for Chemical Engineering (CSChE) and AIChE. He
received a bachelors degree in chemical engineering from Birla
Institute of Technology and Science (BITS, Pilani, India), a masters
degree in environmental engineering from Asian Institute of
Technology (AIT, Bangkok, Thailand), and a doctorate in chemical
engineering from the Univ. of Calgary.