The calculations done by usind the partition coefficient formula as,

The partition coefficient K is the ratio of the compound's concentration in the

organic layer compared to the aqueous layer. Actual partition coefficients are
experimental, but can be estimated by using solubility data.

K = Molarity in organic phase / Molarity in aqueous phase

≈ Solubility in organic phase / Solubility in aqueous phase

The true K represent the equilibrium between aqueous and organic solutions,
while solubility data represent the equilibrium between a saturated solution and
the solid phase.

Now for given example we can calculate K as

K = (5.5 g of caffine in 100 mL of Benzene) / (2.2 g of caffine in 100 mL

water)

K = (5.5/100) /(2.2/100)

K= 5.5/2.2 = 2.5

As K is equilibrium constant it can not be changes and we calculte the extraction

values of caffine as follows,

1) for 200 mL singal extraction from 500 mL of water dissolved 5 g of

caffine

If x is the gram quantity of caffine extracted into the benzene layer, then "5.0
g−x" would remain in the aqueous layer after equilibrium is established. Knowing
the value of K, the value of x can be solved for using the equation below

K = (x/200) / ((5-x) /500)

2.5 = 5x / 2(5-x) = 5x / (10-2x)

25-5x =5x

10x = 25

x = 2.5 g

Means 2.5 g (50%) is extracted in singal extraction of 200 mL of benzene.

2) for two succesivev 100mL extraction from 500 mL of water dissolved 5 g
of caffine

As before, we can assign the quantity of caffine extracted into the benzene the
value "x", which would leave "5 g − x" remaining in the aqueous layer of the first
extraction. Using K, the calculation is identical to the previous discussion,
differing only in the smaller volume of the organic layer (100mL instead of
200mL).

K = (x/100) / ((5-x) /500)

2.5 = 5x / (5-x) =

5x = 12.5 - 2.5x

7.5x = 12.5

x = 1.66 g

means that 1.66 g is extracted into the benzene in the 2nd extraction and 3.34 g
remains in the aqueous layer (5g-1.66g). As the aqueous layer is returned to the
separatory funnel, the residual 3.34 g is the quantity to be further extracted,
which alters the calculation for the second extraction by replacing the 5g value.

K = (x/100) / ((3.34 - x) /500)

2.5 = 5x / (3.34-x) =

8.35 - 2.5x = 5x

7.5x = 8.35

x = 1.11 g

This result means that 1.11 g is extracted into the benzene in the second
extraction

Thats means combined total 2.77 g (55.40%) was extracted in 100 mL of

benzene in two successful extraction.

3) for 66.6 mL three succesive extraction from 500 mL of water dissolved 5

g of caffine

As before, we can assign the quantity of caffeine extracted into the benzene the
value "x", which would leave "5 g − x" remaining in the aqueous layer of the first
extraction. Using K, the calculation is identical to the previous discussion,
differing only in the smaller volume of the organic layer (66.6 mL instead of
100mL).

K = (x/66.6) / ((5-x) /500)

2.5 = 5x / 0.67(5-x) = 5x / 3.35 -0. 67x

5x = 8.375 - 1.675x

6.675x = 8.675

x = 1.3 g

means that 1.3 g is extracted into the benzene in the first extraction and 3.7 g
remains in the aqueous layer (5g-1.3 g). As the aqueous layer is returned to the
separatory funnel, the residual 3.7 g is the quantity to be further extracted, which
alters the calculation for the second extraction by replacing the 5g value.

K = (x/66.6) / ((3.7- x) /500)

2.5 = 5x / 0.66(3.7 - x) =5x / 2.44 - 0.66x

5x = 6.1- 1.675x

6.675x = 6.1

x = 0.91g

means that 0.91 g is extracted into the benzene in the 2nd extraction and 2.79 g
remains in the aqueous layer (3.7g - 0.91 g). As the aqueous layer is returned to
the separatory funnel, the residual 2.79 g is the quantity to be further extracted,
which alters the calculation for the second extraction by replacing the 5g value.

K = (x/66.6) / ((2.79- x) /500)

2.5 = 5x / 0.66(2.79- x) =5x / 1.87- 0.66x

5x = 4.67- 1.675x

6.675x = 4.67

x = 0.7 g
means that 0.7 g is extracted into the benzene in the 3rd extraction and 2.09g
remains in the aqueous layer.

Thats means combined total 2.91g (58.20%) was extracted in 66.6 mL of

benzene in three successful extraction.