1

ABSTRACT

The process of liquid/gas absorption is used in many chemical industries for purifying a gas
stream. The main objective of the experiment was to determine the rate of absorption of carbon
dioxide into water. This was achieved by titrating samples of water entering and exiting the
absorption column, at different time intervals, to determine the amount of carbon dioxide they
contained. In this experiment, the water was continuously recycled through the absorption
apparatus. As such, it was found that over time, the amount of carbon dioxide in the water
increased, but the rate at which the carbon dioxide was absorbed decreased.
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OBJECTIVES

Absorption is the taking up of matter in bulk by other matter, as in the dissolving of a gas in a
liquid [1]. Liquid/gas absorption is a process used in many chemical industries. For instance,
liquid/gas absorption can be used to remove acidic gases (H2S, CO, CO2) from gases being
released into the atmosphere – to limit acid rain. The removal of ammonia from the product
stream of the Haber process utilizes the gas/liquid absorption process [2].

The main objective of this experiment is to calculate the rate of absorption of carbon dioxide
into water, from analysis of liquid solutions flowing down the absorption column. The
absorption of carbon dioxide into water is a mass transfer operation. It is important for chemical
engineers to be able to determine how fast a process can operate so that an operating time is
calculated. In particular, it is important for the rate of a mass transfer operation to be determined
so that the time necessary for a specified amount of mass transfer to occur.
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APPARATUS/PROCEDURE

List of equipment and materials used to conduct the experiment:

o The ARMFEILD gas/liquid absorption column

o Measuring cylinders

o Conical flasks

o Burettes

o Funnel

o White tile

o Distilled water

o Tap water

o Carbon dioxide gas

o Phenolphthalein indicator

o 0.0277M sodium hydroxide solution

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Figure 1 is a sketch of the ARMFIELD absorption apparatus used to determine the rate of
absorption of carbon dioxide from air into water. Sampling points for collecting S4 and S5are
clearly indicated in figure 1. The absorption apparatus required the use of water (supplied from
sump tank), a supply of carbon dioxide gas, and a source of air (air was taken in through the
compressor from the surroundings).

Figure 2 is a picture of the ARMFEILD gas/liquid absorption column equipment [3].

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Figure 3 shows the set up of apparatus for carrying out titrations on the samples collected from
the sump tank and the sampling point at the base of the column.

The procedure followed in conducting the experiment:

1. The sump tank was filled to ¾ its volume, VT = 37.5L, with water.

2. With the air flow and carbon dioxide flow valves closed, the pump was started and the
water flow rate was set to 6 L min-1.

3. The air flow valve was opened to allow an air flow rate of 20 L min-1 through the
absorption column.

4. The carbon dioxide valve was opened for carbon dioxide to flow up through the
column, with the air, at half the air flow rate- i.e. 10 L min-1.
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5. After 15 minutes of the mixture of carbon dioxide and air, counter-flowing water
through the packed column, a sample (S5) of water from the sump tank and a sample
(S4) from the sampling point at the base of the column (sampling point is indicated in
figure 1), was taken.

6. Five more sets of samples (S4 and S5) were taken at 10-minute intervals.

7. 100ml of each sample collected, was measured using a measuring cylinder, and titrated
with 0.0277M sodium hydroxide solution. Eight drops of phenolphthalein were added
to the 100ml of sample, in a conical flask, before titrating. The end-point of the titration
was indicated by an onset of pink coloration of the solution in the conical flask.

8. The volume of sodium hydroxide used in each titration (VB) was recorded.
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THEORY

Mass transfer operations involve the changes in composition of solutions (or phases) [4] and it
occurs because of concentration differences. The solute (the substance being transferred between
phases) moves from a region of high concentration to one of low concentration. The rate of
diffusion within a phase is dependent on the concentration gradient in the phase [4]; and
diffusion occurs until the system comes into a state of equilibrium. In the experiment conducted,
the solute is carbon dioxide, which transfers from the gas phase (air and carbon dioxide mixture)
to the liquid phase (water).

The purpose of a packed column is to provide sufficient contact time between phases to allow
mass to transfer between the phases [4]. The mass transfer of carbon dioxide from air to water is
a situation of the transfer of a substance to a non-transferring substance. That is, there is no
counter-transfer, and the situation can be compared to that of diffusion of a substance through a
stagnant liquid. For such circumstances and steady state operation, the molar rate of diffusion [4]
of the substance is given by:

NA = ky (yA,g – yA,i) = kx (xA,i – xA,l)

Where; A_ the substance being transferred,

ky, kx_ mass transfer coefficient in gas phase and liquid phase, respectively,

yA,g, yA,i _ mole fraction of A in the gas, and at the gas-liquid interface, respectively, and

(yA,g – yA,i) _ the driving force in the gas phase,

xA,i, xA,l _ mole fraction of A at the liquid-gas interface, and in the liquid, respectively,
and (xA,i – xA,l) _ the driving force in the liquid phase.

This equation shows that the rate of mass transfer of A (carbon dioxide), depends on the
concentration gradients of A within each phase. The greater the concentration gradient, the
greater the rate of absorption of carbon dioxide into the water.
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In this experiment, not enough measurements was taken for the rate of absorption to be
determined from the previous equation. Also, as the water is recycled in this experiment this
makes the use of the previous equation more difficult. Instead, the absorption rate for carbon
dioxide across the column at any given time is given by:

Absorption rate = (inlet flow of dissolved CO2) – (outlet flow of dissolved CO2)

= (F × CD(5,i)) – (F × CD(4,i)).

The average rate of absorption over a given period, t was given by:

Average rate = [(amount of CO2 absorbed over a period t) (VT) / t], where t is in seconds.
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RESULTS/DISCUSSION

Table 1 shows flow rates of water, air, and carbon dioxide through the absorption column; and
the volume of water in the sump tank, (VT).

VT, L 37.5

Water Flow Rate, L min-1 6

Air Flow rate, L min-1 20

Carbon dioxide flow rate, L min-1 10

Table 2 shows titration results for the sump water samples (S5), and samples collected at the
sampling point at the base of the column (S4). Where VB,4 and VB,5 are the volumes of sodium
hydroxide used to neutralize S4 and S5 samples respectively.

Time Elapsed (mins) S5 Sample VB,5 (ml) S4 Sample VB,4 (ml)

15 S5,1 12.8 S4,1 15.4

25 S5,2 12.5 S4,2 21.1

35 S5,3 17.2 S4,3 26.25

45 S5,4 15.1 S4,4 32.45

55 S5,5 -- S4,5 20.7

65 S5,6 18.9 S4,6 18.25

In conducting the experiment an experimental error occurred in that, indicator, unfortunately,

was not added to the sump sample that was taken after an elapsed time of 55 minutes, before
being titrated. This error was noticed only after too much alkali was added to the sump sample,
to determine the sample’s end-point. Hence an estimation of volume of 0.0277M sodium
hydroxide required to neutralise sample S5,5 is needed.
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However, from table 2, it is difficult to notice a trend in the VB,5 results for the sump samples.
Taking more than one sump and sampling point samples per time interval would give greater
accuracy; since mean volumes of sodium hydroxide needed for neutralization, can then be
calculated for a S4 or S5 at different time intervals.

Now considering what is happening in the absorption apparatus, within each time interval, a
fraction of sump water is passed through the packed column. This fraction of sump water
ALWAYS absorbs some carbon dioxide; hence, the amount of carbon dioxide in the sump water
should always increase with time.

A continuous increase of carbon dioxide concentration in the sump water is not apparent from
the experiment results. This is due to experimental errors on behalf of the experimenter.
Phenolphthalein indicator is colourless in acidic solutions, but pink in alkaline solutions. The
end-point of the titration was indicated by the contents in the conical flask obtaining a light pink
colouration. It was difficult to determine when a solution had just changed colour; and as such,
some solutions, at the end of the titration, would have a more distinct pink colour than others
would. This means than some results for VB are more accurate than others were.

Phenolphthalein has a pH range of 8.3 to 10 [5] so an indicator with a similar pH range can be
used to titrate the strong alkali (0.0277M NaOH) with a weak acid (water with dissolved CO2). A
suitable replacement for phenolphthalein is thymol-blue indicator with a pH range of 8 to 9.6.
This indicator is yellow in acidic solutions and blue in alkaline solutions. Hence, a very
distinctive green colouration would indicate the end-point.

To determine if the increase for carbon dioxide in the sump water is linear or otherwise, the
results were compared with another group’s results – group L results (shown in table 3 below).

Table 3 shows group L titration results for samples collected.

Time Elapsed (mins) S5 Sample VB,5 (ml) S4 Sample VB,4 (ml)

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15 S5,1 22.4 S4,1 24

25 S5,2 29.0 S4,2 31.9

35 S5,3 29.2 S4,3 36.1

45 S5,4 33.9 S4,4 36.0

55 S5,5 34.1 S4,5 34.4

65 S5,6 35.0 S4,6 34.5

Graph 1 showing group L titration results.

The most suitable trend found for group L’s VB,5 results with respect to time is a linear one.
Hence a linear relationship of VB,5 results with respect to time will also be found (for GROUP F
experiment results); and used to determine the amount of 0.0277M sodium hydroxide required to
neutralise the S5,5 sample.
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Graph 2 shows titration trends for the experiment conducted (by group F); specifying a linear
relation of the volume of 0.0277M NaOH used to neutralise the sump water samples with time.

Now, both graphs 1 and 2 show a rapid increase in VB,4 values with time, followed by a
decrease. The reason for the decrease in the trend of VB,4 values is that, with time, the inlet water,
to the absorption column, contains more carbon dioxide. Accordingly, the driving force for the
mass transfer of carbon dioxide, the concentration gradient with respect to the liquid phase, is
therefore increasingly smaller with time (the concentration gradient in the gas phase is relatively
constant). This is in agreement with the theory.

Now the initial increase in the trend of VB,4 values can be explained by considering the flow
rates of gases and water. The carbon dioxide at a flow of 10 Lmin-1 was mixed with an air flow
rate of 20 Lmin-1. This means that the stream of gas flow through the absorption apparatus is not
very concentrated with carbon dioxide. Carbon dioxide, when compared with air, is more soluble

in water. However, carbon dioxide is still only sparingly soluble in water. So with a water flow
rate of 6 Lmin-1 only small amounts of carbon dioxide is absorbed with time. This small increase
in carbon dioxide in the liquid phase is too insignificant to decrease the driving force, with
respect to the liquid phase, for a noticeable decrease in the absorption rate. However, the initial
small increase is significant enough to add to the carbon dioxide that was absorbed in the water,
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to increase the volume of sodium hydroxide needed for neutralisation. Hence the initial increase
in VB,4 values.

CALCULATIONS/DISCUSSION

Determining a value for VB,5 corresponding to sample S5,5.

Using the relation shown in graph 2, when the time elapsed is 55 minutes, that is x = 55, then

y = 0.1243x +10.7

y = 0.1243(55) + 10.7

y = 17.5

Hence, the volume of sodium hydroxide used to neutralise the sump sample collected after 55
minutes is 17.5 ml.

Calculating the moles of carbon dioxide per litre of sample:

The stoichiometric equation of the reaction of carbon dioxide in the water with the sodium
hydroxide is CO2 + 2NaOH → Na2CO3 + H2O.

Moles of sodium hydroxide used in titration = VB × (NaOH molarity).

Mole ratio of carbon dioxide to sodium hydroxide is 1:2.

Moles of carbon dioxide in sample = ½ [VB × (NaOH molarity)].

Therefore, mole/litre of free CO2, CD = ½ [VB (ml) × 0.0277(mol L-1)] / 100 (ml).

Sample calculation:

For sample S5,1, VB = 12.8 ml.

CD(5,1) = ½ [12.8 (ml) × 0.0277(mol L-1)] / 100 (ml).

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= 1.773 × 10-3 mol L-1.

Table 3 shows experiment results along with the amount of carbon dioxide per mole of solution
is contained in samples collected

Time Elapsed CD(5) CD(4)

S5 Sample VB,5 (ml) S4 Sample VB,4 (ml)
(mins) (mol/L) (mol/L)

15 S5,1 12.8 0.001773 S4,1 15.4 0.002133

25 S5,2 12.5 0.001731 S4,2 21.1 0.002922

35 S5,3 17.2 0.002382 S4,3 26.25 0.003636

45 S5,4 15.1 0.002091 S4,4 32.45 0.004494

55 S5,5 17.5 0.002424 S4,5 20.7 0.002867

65 S5,6 18.9 0.002618 S4,6 18.25 0.002528

Calculating the amount of carbon dioxide dissolved over different time intervals:

Sample calculation:

Considering the S5 samples, for a time interval of 20 minutes;

Average rate = [(CD(5,3) – CD(5,1)) (VT)] / (20 × 60)

= [(0.002382 – 0.001773) (37.5)] / (20 × 60)

= 19.03 × 10-6 mol s-1.

Table 4 shows average rate of absorption of carbon dioxide over different time intervals for
sump (S5) samples and sampling point (S4) samples.

Time Interval (min) Average Rate for S5 (mol/s) Average Rate for S4 (mol/s)

10 -2.59688 × 10-6 4.93406 × 10-5

20 1.90438 × 10-5 4.69602 × 10-5
30 6.63646 × 10-6 4.91964 × 10-5
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40 1.01711 × 10-5 1.14695 × 10-5

50 1.05606 × 10-5 4.93406 × 10-6

Graph 3 shows the absorption rate of carbon dioxide over different time intervals with respect to
the sump water (S5) samples and sampling point (S4) samples.

Graph 3 simply reflects graph 2 and the experiment results. The average rate for S4 values
relation shows a decrease in the rate of absorption, of carbon dioxide, with time, as the driving
force in the liquid phase decreases. This was previously explained in examining graph 2. The
average rate for S5 values relation reflects a slowing increase in carbon dioxide absorption with
time. This is because while the amount of carbon dioxide in the sump water increases, less
carbon dioxide is absorbed with time.

Calculating the absorption rate of carbon dioxide in the column at any time:

Absorption rate = (inlet flow of dissolved CO2) – (outlet flow of dissolved CO2)

= (F × CD(5,i)) – (F × CD(4,i))

= F (CD(5,i) – CD(4,i))
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Sample calculation:

For samples taken after an elapsed time of 35 minutes;

Absorption rate = F (CD(5,3) – CD(4,3))

= (6/60) L s-1 × (0.002382 - 0.003636) mol L-1

= - 125.4 × 10-6 mol s-1.

Table 5 shows the rate of absorption of carbon dioxide across the column at any time.

Time Interval (min) Absorption Rate (mol/s)

15 -0.00003601

25 -0.00011911

35 -0.000125343

45 -0.000240298

55 -0.00004432

65 9.0025 × 10-6
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Graph 4 shows the rate at which carbon dioxide is absorbed across the column at any time.

The negative absorption rate is due to the values for VB,5 being smaller than the values for VB,4 –
except the VB,5 corresponding to sample S5,6. Now, the water in the sump tank at any particular
time during the operation of the absorption apparatus has a greater amount of carbon dioxide
than the volume of water in the packed column at that time. However, because of the greater
amount of water in the sump tank, the carbon dioxide from a sump water sample would be of a
small concentration. The increasing negative portion of graph 4 corresponds with the increasing
portion of the VB,4 relation with time intervals, in graph 2. This suggests that initially the
concentration of carbon dioxide in the S4 samples increases greatly when compared with the
increase in the S5 (sump water) samples. The decreasing negative portion of graph 4 is due to the
decreasing ratio of concentration of carbon dioxide in S4 to that in S5, as rate of absorption of
carbon dioxide decreases with time.
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CONCLUSIONS/RECOMMENDATIONS

The rate of absorption of carbon dioxide into water was determined by titrating samples of water
entering and exiting the absorption column, at different time intervals, to determine the amount
of carbon dioxide they contained. As the water used was recycled, it was found that the total
amount of carbon dioxide in the water, increased with time. The rate of absorption of the carbon
dioxide into the water depended on the concentration of carbon dioxide already in the water. It
was shown that the rate of the absorption of the carbon dioxide, into the water, decreased with
time.

Possible improvements to increase the accuracy in the results for this experiment is to take more
than one sump sample and more than one sampling point sample for each time; and to use
another indicator – thymol blue.
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REFERENCES

[1] Cited 27th September 2009. Available from the internet:

<http://encyclopedia2.thefreedictionary.com/Absorption>

[2] Cited 27th September 2009. Available from the internet:

<http://www.uic.edu/depts/chme/UnitOps/CO2.pdf>

[3] Cited 27th September 2009. Available from the internet:

<http://www.armfield.co.uk/uop7_datasheet.html>

[4] Treybal, R.E. (1980). Mass Transfer Operations (3rd edition). McGraw-Hill, New York.

[5 ] Cited 27th September 2009. Available from the internet:

<http://www.ausetute.com.au/indicata.html>
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APPENDIX