TITLE: BATCH REACTOR

Objective:

1. To determine the reaction rate of saponification reaction at given temperature

by measuring the conversion against reaction time.
2. To evaluate the reaction rate constant at constant temperature using
differential and integral methods of analysis.
3. To evaluate the rate constant at different temperatures and activation energy
determination from Arrehenius Plot.

Introduction:

A batch reactor is a vessel in which the chemicals are placed to react. Batch reactors
are normally used in small- scale laboratory set-ups to study the kinetics of chemical
reactions. The variation of a property of the reaction mixture is observed as the
reaction progresses in order to determine the order and rate constant of a chemical
reaction. Data collected consist of concentration of the component, volume of the
system and physical property like electrical conductivity.

Theory :

For any given reaction in a constant volume system, the rate of the reaction can be
represented by:

𝑑𝐶𝐴
−𝑟𝐴 = 𝑘𝑓(𝐶𝐴 ) = − … … (1)
𝑑𝑡

Where 𝑟𝐴 is the rate of disappearance of reactant A among the reacting species.

Equation (1) can be rearranged to give:

𝑑𝐶𝐴
− = 𝑘𝑑𝑡 … … (2)
𝑓(𝐶𝐴 )

Integrating the equation (2) analytically yields

 𝐶𝐴𝑓 𝑡
𝑑𝐶𝐴
−∫ = 𝑘 ∫ 𝑑𝑡 = 𝑘𝑡 … … (3)
𝐶𝐴𝑜 𝑓(𝐶𝐴 ) 0

By postulating various forms for 𝑓(𝐶𝐴 ) in equation (3) and correlating the resulting
equation with the experimental data, the rate constant k, and order of the reaction can
be determined assuming that the rate of reaction can be expressed by an equation of
form:

−𝑟𝐴 = 𝑘𝐶𝐴𝑛 … … (4)

The values of n and k can determined experimentally.

Differential method of analysis

 Hypothesize a rate equation. For example equation (4), −𝑟𝐴 = 𝑘𝐶𝐴𝑛 where n is
the assumed order.
 Obtain concentration (𝐶𝐴 ) versus time data from batch experiments. Draw 𝐶𝐴
𝑑𝐶𝐴
vs time. Draw tangents at various points. Find the slopes, these slopes are 𝑑𝑡

are the rate of reaction (−𝑟𝐴 ) at these concentrations.

 Taking logs on both sides of the rate equation will give ln(−𝑟𝐴 ) = ln 𝑘 + 𝑛.
 Plot of ln(−𝑟𝐴 ) vs ln(−𝐶𝐴 ) will give a straight line with slope n (order) if the
assumed form of rate equation is correct. k may be obtained from the intercept.

The reaction rate, r is generally depend on the reactant concentration and rate constant
(k). The rate constant can be determined by using a known empirical reaction rate that
is adjusted for temperature using the Arrhenius temperature dependence. Generally, as
the temperature increase so does the rate at which the reaction occurs. The
temperature dependency of rate is given by Arrhenius equation:

−𝐸
𝑘 = 𝑘𝑜 𝑒 𝑅𝑇

Where k is the rate constant, 𝑘𝑜 is the frequency factor, E is the activation energy, R is
the gas constant, T is absolute temperature.
Materials and Equipment:

1. Beaker: 2L × 1, 1L × 1, 250mL × 2
2. Measuring Cylinder: 100mL × 2
3. Glass rod
4. Conductivity meter
5. Electric stirrer
6. Water bath
7. Stopwatch
8. 5 L of 0.1 M sodium hydroxide, NaOH
9. 2 L of 0.1 M ethyl acetate, Et(Ac)
10. 500mL of 0.1 M sodium acetate, Na(Ac)
11. 1 L of deionized water, H20

Setup:

Figure 1: Setup of Batch reactor

RESULT:

Experiment 1: Calibration Curve

Conversion (%) NaOH (mL) Et Ac( mL) water( mL) Conductivity (ms)
0 100 0 100 9.23
25 75 25 100 8.50
50 50 50 100 5.51
75 25 75 100 2.42
100 0 0 100 0.0081
Table 1: Conductivity at different conversion

Graph of Calibration curve of Conductivity,

mS/cm vesus Conversion,%
12
Conductivity, (mS/cm)

10
8 y = -0.0981x + 10.038
R² = 0.9718
6
4
2
0
0 20 40 60 80 100 120
conversion, (%)

Graph 1: Calibration curve of Conductivity versus Conversion

 Experiment 2: Rate of Reaction

conductivity (mS/cm)
Time(min) 35°C 45°C 55°C 65°C
0 19.2 13.24 12.31 11.89
3 7.92 7.18 7.16 6.51
6 7.15 7.02 6.79 6.34
9 6.77 6.71 6.69 6.30
12 6.6 6.57 6.63 6.28
15 6.52 6.49 6.61 6.28
18 6.45 6.45 6.59 6.27
Table 2.1: Conductivity at different temperature and time

2.1: For integral method

35°C 45°C 55°C 65°C

Time(min) X CA (M) 1/CA (M-1) X CA (M) 1/CA (M-1) X CA (M) 1/CA (M-1) X CA (M) 1/CA (M-1)
0 0.0000 0.1000 10.0000 0.0000 0.1000 10.0000 0.0000 0.1000 10.0000 0.0000 0.1000 10.0000
3 0.2159 0.0784 12.7535 0.2913 0.0709 14.1110 0.2934 0.0707 14.1518 0.3596 0.0640 15.6160
6 0.2944 0.0706 14.1722 0.3076 0.0692 14.4435 0.3311 0.0669 14.9497 0.3770 0.0623 16.0504
9 0.3331 0.0667 14.9954 0.3392 0.0661 15.1342 0.3413 0.0659 15.1811 0.3810 0.0619 16.1561
12 0.3505 0.0650 15.3955 0.3535 0.0646 15.4683 0.3474 0.0653 15.3233 0.3831 0.0617 16.2095
15 0.3586 0.0641 15.5912 0.3617 0.0638 15.6659 0.3494 0.0651 15.3714 0.3831 0.0617 16.2095
18 0.3657 0.0634 15.7666 0.3657 0.0634 15.7666 0.3515 0.0649 15.4197 0.3841 0.0616 16.2363
Table 2.2: calculated parameters for rate constant of integral method

Rate of reaction
Temperature Rate constant, k (M/min)
35°C 0.2881 0.0029
45°C 0.2552 0.0026
55°C 0.2270 0.0023
65°C 0.2388 0.0024
Table 2.3: Calculated rate constant and rate of reaction using integral method
 Temperature Time taken (min)
35°C 659.5
45°C 744.5
55°C 837.0
65°C 795.6
Table 2.4: Time required reaching 95 % conversion

Graph of 1/CA,M-1 versus Time,min

20.0000
18.0000 y = 0.2881x + 11.504 (35°C)
16.0000 y = 0.2552x + 12.073 (45°C)
1/CA , M-1

14.0000
y = 0.227x + 12.299 (55°C)
12.0000
y = 0.2388x + 13.062 (65°C)
10.0000
8.0000 AT 35°C
6.0000 AT 45°C
4.0000 AT 55°C
2.0000 AT 65°C
0.0000
0 5 10 15 20
Time, min
Graph 2.1: 1/CA, M-1 versus Time, min
 2.2: For differential method

35°C 45°C 55°C 65°C

Time(min) CA (M) ln CA (-dCA/dt) ln(-dCA/dt) CA (M) ln CA (-dCA/dt) ln(-dCA/dt) CA (M) ln CA (-dCA/dt) ln(-dCA/dt) CA (M) ln CA (-dCA/dt) ln(-dCA/dt)
0 0.1000 -2.3026 0.0051 -5.2785 0.1000 -2.3026 0.0051 -5.2785 0.1000 -2.3026 0.0053 -5.2400 0.1000 -2.3026 0.0059 -5.1328
3 0.0784 -2.5458 0.0039 -5.5468 0.0709 -2.6470 0.0039 -5.5468 0.0707 -2.6498 0.0041 -5.4968 0.0640 -2.7483 0.0047 -5.3602
6 0.0706 -2.6513 0.0027 -5.9145 0.0692 -2.6702 0.0027 -5.9145 0.0669 -2.7047 0.0029 -5.8430 0.0623 -2.7757 0.0035 -5.6550
9 0.0667 -2.7077 0.0015 -6.5023 0.0661 -2.7170 0.0015 -6.5023 0.0659 -2.7200 0.0017 -6.3771 0.0619 -2.7823 0.0023 -6.0748
12 0.0650 -2.7341 0.0003 -8.1117 0.0646 -2.7388 0.0003 -8.1117 0.0653 -2.7294 0.0005 -7.6009 0.0617 -2.7856 0.0011 -6.8124
15 0.0641 -2.7467 -0.0009 - 0.0638 -2.7515 -0.0009 - 0.0651 -2.7325 -0.0007 - 0.0617 -2.7856 -0.0001 -
18 0.0634 -2.7579 -0.0021 - 0.0634 -2.7579 -0.0021 - 0.0649 -2.7356 -0.0019 - 0.0616 -2.7873 -0.0013 -

Table 2.4: calculated parameters for rate constant of differential method

Temperature Oder of reaction rate constant, k rate of reaction (M/min)

35°C 4.7822 449.0346 0.0074
45°C 4.0714 79.5511 0.0067
55°C 3.2498 11.1039 0.0062
65°C 1.928 1.9005 0.0224
Table 2.5: Calculated rate constant and rate of reaction using differential method

Temperature Time taken (min)

35°C 0.4
45°C 2.4
55°C 17.1
65°C 100.0
Table 2.6: Time required reaching 95 % conversion
 Graph of CA (M) vesusTime(min)
0.1200
y = 0.0002x2 - 0.0051x + 0.0966 (35°C)
0.1000
y = 0.0002x2 - 0.0051x + 0.0939(45°C)
0.0800
y = 0.0002x2 - 0.0053x + 0.0937 (55°C)
CA (M)

0.0600
y = 0.0002x2 - 0.0059x + 0.0917(65°C)
0.0400
35°C
0.0200 45°C
0.0000 55°C
0 5 10 15 20 65°C
Time(min)

Graph 2.2: CA (M) vesusTime(min)

Graph of ln(-dCA/dt) vssus ln CA

-4.5000
y = 4.7822x + 6.1071(35°C)
-3.0000 -2.8000 -2.6000 -2.4000 -2.2000 -2.0000
-5.0000
y = 4.0714x + 4.3764(45°C)
-5.5000
ln(-dCA/dt)

y = 3.2498x + 2.4073(55°C)
-6.0000
y = 1.928x - 0.6421(65°C)
-6.5000

-7.0000
35°C
-7.5000 45°C
-8.0000 55°C
ln CA 65°C

Graph 2.3: Graph of ln(-dCA/dt) versus ln CA

Calculation:

Concentration of NaOH, 𝐶𝐴 = 0.1 mol/L

Second order reaction:

−𝑟𝐴 = 𝑘𝐶 2 − − − − − − − − − − − − − −−→ (1)

In this reaction, since

𝐶𝐴 = 𝐶𝐵

Thus,

−𝑟𝐴 = 𝑘𝐶𝐴 2 − − − − − − − − − − − − − −→ (2)

-
The OH ion is the most highly conductive species, thus ethyl acetate may be ignored.

𝐶𝐴 = (1 − 𝑋) × 𝐶𝐴0 − − − − − − − − − −→ (3)

Where X is the fractional conversion of NaOH,

Integral method,

For a second order reaction with equimolar concentration, the fractional conversion is
related to the reaction rate constant by

1 1
= + 𝑘𝑡 − − − − − − − − − − − −−→ (4)
𝐶𝐴 𝐶𝐴0

Figure2: Graph of Second order reaction for integral method

Differential method,

−𝑟𝐴 = 𝑘𝐶 𝛼

Where the 𝛼 is the order of reaction

For a second order reaction with equimolar concentration, the fractional conversion is
related to the reaction rate constant by

𝑑𝐶𝐴
ln (− ) = ln(−𝑟𝐴 ) = ln 𝑘 + 𝛼 ln 𝐶𝐴
𝑑𝑡

𝑑𝐶𝐴
is found from CA vs t by polynomial method
𝑑𝑡

𝑑𝐶𝐴
ln (− ) vs ln CA is plotted for the reaction order 𝛼, which is the slope of the line fit
𝑑𝑡

to the data. Thus, rate constant, k can be determined.

Sample calculation:

1) For temperature = 35 °C

At t= 3 min, the conductivity is 7.92 mS

Using integral method,

Using the line equation of calibration curve,

𝑦 = −0.0981𝑥 + 10.038

10.038 − 𝑦
𝑋=
0.0981

= 0.2159

𝐶𝐴 = (1 − 𝑋) × 𝐶𝐴0

= (1 − 0.2159) × 0.1𝑀

= 0.0784 M

1
= 12.7535 𝑀−1
𝐶𝐴

1
From the Graph of versus time plotted,
𝐶𝐴

The rate constant at 35°C, k = 0.2881 𝑀−1 𝑚𝑖𝑛−1

Rate of reaction

−𝑟𝐴 = 𝑘𝐶𝐴 2

= 0.2881 𝑀−1 𝑚𝑖𝑛−1 (0.1𝑀)2

= 0.002881 𝑀𝑚𝑖𝑛−1
Using differential method

From the CA vs t, the polynomial equation is y = 0.0002x2 - 0.0051x + 0.0966

𝐶𝐴 = 0.0002𝑡 2 − 0.0051𝑡 + 0.0966

𝑑𝐶𝐴
= 0.0004𝑡 − 0.0051
𝑑𝑡

𝑑𝐶𝐴 𝑑𝐶𝐴
From , the graph of ln (− ) vs ln CA is plotted,
𝑑𝑡 𝑑𝑡

𝑦 = 4.7822𝑥 + 6.1071

Compare with

𝑑𝐶𝐴
ln (− ) = ln 𝑘 + 𝛼 ln 𝐶𝐴
𝑑𝑡

ln 𝑘 = 6.1071

𝑘 = 449.03 𝑀−1 𝑚𝑖𝑛−1

Rate of reaction

−𝑟𝐴 = 𝑘𝐶𝐴 𝛼

= 449.03 𝑀−1 𝑚𝑖𝑛−1 (0.1𝑀)4.7822

= 0.0074 𝑀𝑚𝑖𝑛−1

2) Time required to reach 95% conversion

1 1
= + 𝑘𝑡
𝐶𝐴 𝐶𝐴0

1 1
= + 0.2881 𝑡
(1 − 0.95)(0.1) 0.1

200 − 10
𝑡= = 659.49 𝑚𝑖𝑛
0.2881
3) Activation energy determination from Arrehenius plot

−𝐸𝑎
𝑘(𝑇) = 𝐴𝑒 𝑅𝑇

𝐸𝐴 1
ln 𝑘 = − ( ) + ln 𝐴
𝑅 𝑇

𝑦 = 𝑚𝑥 + 𝑐

k (M-1 min-1) ln k T (°C) T ( K) 1/T

0.2881 -1.2444 35.0000 308.1500 0.0032
0.2552 -1.3657 45.0000 318.1500 0.0031
0.2270 -1.4828 55.0000 328.1500 0.0030
0.2388 -1.4321 65.0000 338.1500 0.0030
Table 3: Calculated parameters for activation energy using Arrhenius plot
 Graph of ln k vs 1/T
-1.2000
0.0029 0.0030 0.0030 0.0031 0.0031 0.0032 0.0032 0.0033 0.0033
-1.2500 0.0032, -1.2444

-1.3000
ln k

-1.3500
0.0031, -1.3657
-1.4000
y = 719.29x - 3.6098
0.0030, -1.4321
-1.4500
0.0030, -1.4828
-1.5000
1/T

Graph 3: Graph of ln k versus EA/R

By plotting the graph ln k versus EA/R,

𝐸𝐴 1
Compare the equation y = 719.29x – 3.6098 and ln 𝑘 = − (𝑇) + ln 𝐴,
𝑅

We know that

−𝐸𝐴
𝑚= = 719.29
𝑅

𝐽
𝐸𝐴 = −5980.18
𝑚𝑜𝑙

𝐾𝐽
𝐸𝐴 = −5.98
𝑚𝑜𝑙

And

ln 𝐴 = −3.699

𝐴 = 0.0247 𝑀 −1 𝑚𝑖𝑛−1
DISCUSSION:

From the experiment 2, the rate of reaction of ethyl acetate, Et(Ac) and sodium
hydroxide, NaOH has been studied. The saponification of ethyl acetate and sodium
hydroxide will produce sodium acetate and ethanol. The reading from the
conductivity meter is due to the OH- ions. As the reaction proceed with time, the
conductivity of the mixture of Et(Ac) and NaOH will decrease with time as shown in
Table 2.1 for 35 °C ,45 °C , 55 °C and 65 °C respectively. The reason cause the
decrease of conductivity is because with the progress of the reaction, highly
conducting OH− ions in the solution were replaced by an identical number of less
conducting acetate ions resulting in a continuous decrease in conductivity of solution.
(Das, Sahoo, Magapu, & Swaminathan, 2011)

Besides, the conversion, X increase as the time proceed as more reactants are being
converted to the products. Theoretically, the rate constant, k and the rate of reaction
should increase when the temperature of saponification reaction is increased by
interval of 10 °C from 35 °C to 65 °C. However, the result we obtained is not same
with the expected result as the rate constant and rate of reaction show in table 2.3 is a
decreasing trend with the increased of temperature. At high temperature, more kinetic
energy is provided to the reactants to increase the probability of collision between
reactant molecules and overcome the activation energy to form the products. The
error in our result may due to the insensitivity of conductivity meter to detect the
conductivity changes in the solution as the reaction at high temperature (55 °C &
65 °C) is considerably fast. Therefore, error in the conductivity will lead to false rate
constant and rate of reaction. By compare the integral method and differential method,
the order of the saponification reaction calculated by using integral method is 2 while
the order calculated by using differential method is not equal to 2. This indicate
differential method is less accurate and the error can be avoid if large amount and
accurate data is provided when differential method is being used.

The activation energy, 𝐸𝐴 has been evaluated from the Arrehenius plot ( Graph 3 )
𝐾𝐽
The activation energy is −5.98 𝑚𝑜𝑙 , the negative sign indicate the saponification

reaction is an exothermic reaction.

The rate constants for forward and reverse reaction treating the saponification
reaction as reversible reaction

In this experiment, the saponification of ethyl acetate and sodium hydroxide is a

reversible reaction. The forward reaction is very fast once the ethyl acetate mixed
with sodium hydroxide. The forward reaction happened faster than the reverse
reaction until it reaches equilibrium. The reaction of saponification is given as shown:

𝐶4 𝐻8 𝑂2 + 𝑁𝑎𝑂𝐻 ↔ 𝐶2 𝐻4 𝑂2 𝑁𝑎 + 𝐶2 𝐻6 𝑂

At equilibrium state, the forward and reverse reaction is balance and there is no net
change in concentration of reactant and product.

𝑟𝑓𝑜𝑟𝑤𝑎𝑟𝑑 = 𝑟𝑟𝑒𝑣𝑒𝑟𝑠𝑒

By substituting the rate law for the forward and reverse reaction:

𝑘𝑓𝑜𝑟𝑤𝑎𝑟𝑑 [𝐶4 𝐻8 𝑂2 ][𝑁𝑎𝑂𝐻] = 𝑘𝑟𝑒𝑣𝑒𝑟𝑠𝑒 [𝐶2 𝐻4 𝑂2 𝑁𝑎][𝐶2 𝐻6 𝑂]

The forward and reverse rate constant are both constants, so the ratio of forward rate
constant to reverse rate constant can be known as equilibrium constant.

𝑘𝑓𝑜𝑟𝑤𝑎𝑟𝑑 [𝐶2 𝐻4 𝑂2 𝑁𝑎][𝐶2 𝐻6 𝑂]

𝐾𝑐 = =
𝑘𝑟𝑒𝑣𝑒𝑟𝑠𝑒 [𝐶4 𝐻8 𝑂2 ][𝑁𝑎𝑂𝐻]

At any rate for forward and reverse reaction, the ratio will remain the same all the
time.

The advantage of the batch reactor for obtaining kinetic data:

 Batch reactor is an economic equipment requirements relatively easy to

use.
 When sufficiently vigorous mixing, film diffusion and sometime particle
diffusion can be eliminated.
 Constant solution solid ratio is readily maintained in some batch reactor
system
 Reaction condition such as pH, ionic strength and removal of CO2 and O2
are easily to controlled.
The disadvantage or limitation of the batch reactor for obtaining kinetic data:

 Desorbed species will be no removed and are allowed to accumulate in the

inherently closed system of the batch reactor. Unless a unidirectional reaction
is being studies, reverse reactions must be taken into account in the data
analysis. The accumulation of desorbed species can sometimes result in
secondary precipitation reactions, which further complicate data analysis.
 The mixing method employed may not produce a uniform suspension of no
sufficient to mass transfer of solute. Furthermore, surface area may be increase
by prolonged mixing be some methods.
 Sampling and phase separation steps are not always uniform and are operator
dependent. In the case of rapid surface reaction, sampling and phase
separation are not rapid enough to follow the reaction.

The most appropriate method of continuously monitoring the concentration of

reactants during saponification reaction

According the research of Das, K., Sahoo, P., Magapu, S. B., & Swaminathan,
P (2011), using pulsating conductivity meter is the more appropriate to monitoring the
concentration of the reactant during the saponification. The conductivity meter is
designed in such a way that the conducticity cell forms a part of a specially designed
logic gate oscillator (LGO) circuit. The frequency of LGO changes with the change in
the ionic conductivity of the solution taken in the ceel. The frequency is directly
related to the conductivity of the solution. In the present case, the instrument is
designed in such a way that with a change in conductivity of the solution by 1 µS cm-1,
there is a change of about 20Hz in pulse frequency. So the data can be monitor the
change of the concentration of the reactant1.
Figure3: the data showing of saponification reaction by pulsating conductivity meter

Precaution

There are some precaution that need to be aware when conduction this experiment.
First, the timer must start once the ethyl acetate solution is completely poured into the
beaker contain 0.1M sodium hydroxide and the initial reading need to be recorded.
Next, prevent the contact of any part of the body into the water bath as it is heated in
high temperature. Other than that, the unit of the conductivity meter must be aware
when the measure of conductivity of the solutions happen because the meter will
show in a smaller unit when the conductivity of the solution is very small.
Furthermore, prevent the contact of the fin of the mechanical overhead stirrer when
the stirrer is in operation as the fin has sharp surface and it is spinning in high
rotational speed which is 250rpm to avoid injuries. Lastly, gloves must be worn all
time to prevent the contact of hands with the chemicals.
Application

Batch reactor needs a certain time to complete a reaction of chemicals, so it need

higher amount of time to produce numbers of product. That’s mean, batch reactor can
only produce small amount of product compare to other reactor. Because of low cost
and easy to operate, batch reactors are usually used in small scale industries. Next,
batch reactor is also uses some small pieces of equipment to produce various kind of
product. For some expensive products, batch reactor can also be used in those
productions. Products such as pharmaceuticals, dyes and dye intermediates are
produced by using batch reactor. Other than that, batch reactors are also used in
manufacture of colorants and margarine which is widely used in our life.

Conclusion:

The results that obtained had successfully calculated reaction rate, reaction rate
constant and activation energy of saponification reaction. Although there are some
errors need to improve, the results that obtained are can be accepted.
REFERENCES:

1. Das, K., Sahoo, P., Magapu, S. B., & Swaminathan, P. (2011, August 25).
Kinetic Studies on Saponification of Ethyl Acetate using an Innovative
Conductivity-Monitoring Instrument with a Pulsating Sensor. Retrieved from
https://www.researchgate.net/publication/229360677_Kinetic_Studies_on_Sap
onification_of_Ethyl_Acetate_Using_an_Innovative_Conductivity-
Monitoring_Instrument_with_a_Pulsating_Sensor

2. Magdi Selim.H and Micheal C. Amacher (1997) Reactivity and transport of

heavy metal in solids.[online] Retrieved from
https://books.google.com.my/books?id=IYThyxERqMgC&pg=PA32&lpg=P
A32&dq=advantage+of+obtaining+kinetic+data+in+a+batch+reactor&source
=bl&ots=M_-
gSANJZx&sig=crG2KC8Xa0I3TAuCVh3wIjUzeQQ&hl=en&sa=X&redir_es
c=y#v=onepage&q=advantage%20of%20obtaining%20kinetic%20data%20in
%20a%20batch%20reactor&f=false
3. CIEC Promoting Science at the University of York, York, UK. (n.d.).
Retrieved June 27 2016, from
http://www.essentialchemicalindustry.org/processes/chemical-reactors.html
4. Reactors design and types: Its advantages and disadvantages. (2015).
Retrieved June 27 2016, from http://chemicalfunda.com/reactors-design-and-
types-its-advantages-and-disadvantages/
5. Gas-Phase Reactions. (n.d.). Retrieved June 27 2016, from
http://chemed.chem.purdue.edu/genchem/topicreview/bp/ch16/equilib.php