Problems

Crystallization
the formation of solid particles within a
homogeneous phase. It may be carried out from a
It is desired to produce Glauber's salt by dissolving 250 kg of sodium sulfate in
1. A saturated solution containing 1500 kg of potassium chloride at 360 K is cooled in an open tank
vapor (formation of solid particles in a vapor, as in snow) 750 kg of water at 80°C and then passing it through a vacuum crystallizer
(liq) melt (solidification from a liquid melt, as freezing of water to ice) to 290 K. If the specific gravity of the solution is 1.2, the solubility of KCl per 100 parts water is
operating at 20°C. Find the percent yield of the crystals and the composition
solution (formation of solid crystals from a solution, as the formation 53.5 at 360 K and 34.5 at 290 K, and neglecting loss of water by evaporation, calculate:
of magma
of Glauber’s salt from Na2SO4 solution). a. The weight of crystals obtained
process whereby a solution is supersaturated so as to cause formation of crystals.
b. The capacity of the tank required
a solution is brought to a concentration above saturation from which solids crystals precipitate out.
L = 3771.03 kg
crystals that separate out pure substances at a F=M=L+C
KCl = 967.29
particular size and controlled by the operating L
H2O = 2803.74 1500 kg + 2803.74 kg = L + 532.71 kg V
conditions. The impurities are left out in the solution.
F360K L = 3771.03 kg xl = 19.4
Its wide use has two - fold basis:
1500 kg KCl
119.4
1. A crystal formed from an impure solution is itself pure (unless mixed crystals occur) kg H2O KCl Balance: Fxf = Cxc + Lxl F 80 deg C m; 20degC
xl=0.1625
2. Crystallization affords a practical way of obtaining pure chemical substance in a C; KCl crystals 250 kg Na2SO4 Solubility = 19.4
532.71 1500 = 532.71 + Lxl Lxl=967.29 750 kg H2O
satisfactory in a satisfactory condition for packaging and storing.
H2O in = H2O out; no evaporation C; Na2SO4 10 H2O
The rate of crystallization involves two distinct actions:
at 360 K, Solubility KCl = 53.5 xc = 142.04
1. The rate of formation of new crystals (nucleation) Solute Balance: 142.04+180
2. The rate of precipitation on crystals already present (crystal growth to macroscopic size )
H2O = 1500 kg100 3771.03 kg sol'nm³ Fxf = mxc = Lxl + Cxc xc=0.4411
53.5 1200 kg
The driving force for both rates is supersaturation. Neither nucleation nor =2803.74 kg H2O at 290 K, Solubility KCl = 34.5 3.1425 m³ tank H2O Balance:
growth can occur in a saturated or undersaturated solution KCl= 2803.74 kg H2O34.5 KCl
Fw = Vw + Mw = Vw + Lw + Cw
100 H2O
Methods of supersaturating the solutions:
1. By cooling
= 967.29 kg KCl Overall:
2. By evaporation of solvent F = V+ M= V + L + C
3. By adiabatic evaporation with cooling
Solute Balance
4. By addition of a third component where the solubility of the solute is sharply reduced 1500 kg KCl = 967.29 kg KCl + C
Enthalpy balance:
5. By addition of a third component which will react with original solute to form an insoluble product. C=532.71 kg KCl
Fhf = Lhs + Chc + VHv = Chc + V
The extent of the supersaturation depends upon
1. The number and shape of crystals upon which precipitation occurs
2. The temperature levels
Fhf = FCf(Tf-Tm)
3. The solution concentration 1000 kg (Cf)(Tf-Tm)
4. The violence of the agitation present 2. 1200 kg of barium nitrate are dissolved in sufficient water to form a saturated solution at 80 oC.
If 5% of the weight of the original solution is lost through evaporation, calculate crop of crystals Cf = Cp of Na2SO4*xf + Cp H20*xw
Heat Effects in a Crystallization Process
The heat effects in a crystallization process can be computed by two methods obtained when the solution is cooled to 20 oC. Cp Na2SO4 =32.8 kcal/kmol x 4.184 kg/kcal x kmol/142.05 kg
= 0.9661 kJ/kg-K
A heat balance can be made in which individual heat effects such as sensible
L Cf = 0.25(0.9661 kJ/kg-K) + 0.75(4.1868 kJ/kg-K)
heats, latent heats, and the heat of crystallization can be combined into an
equation for total heat effects.
V Cf = 3.3816 kJ/kg-K
An enthalpy balance can be made in which the total enthalpy of all leaving
F 80 deg C Fhf = (1000kg)(3.3816 kJ/kg-K)(80-20)K = 202896 kJ
streams minus the total enthalpy of all entering streams is equal to the heat
absorbed from external sources by the process. Ba(NO3)2 = 1200 kg
H20 =
In using heat balance method, it is necessary to make a corresponding mass
balance, since the heat effects are related to the quantities of solids produced Heat of Crystallization = -Heat of solution
through the heat of crystallization. The advantage of the enthalpy - at 80 deg C, Solubility = 27
concentration diagram method is that both heat and mass effects are taken
C
into account simultaneously. This method has only limited use, however, because H2O in feed = 1200 kg Ba(NO3)2100 H2O =817.08 kg Ba(NO3)2 Hs = -18.74x10³ kcalkmol4.184 kJ
of the difficulty in obtaining enthalpy - concentration data.
27 Ba(NO3)2 kmol322.19kcal
Hs = -243.36 kJ/kg
With compounds whose solubility increases with increasing temperature there = 4444.44 kg Hc=243.36 kJ/kg
is an absorption of heat when the compound dissolves which is called the heat
V = 5%F
of solution. In compounds with decreasing solubility as the temperature
increases there is an evolution of heat when solution occurs. When there is no = 5% ( 4444.44+1200)
at 20 deg C, Solubility = 9.2 v = Hv-Hl @20 deg C
change in solubility with temperature, there is no heat effect. = 282.22 kg H2O
Ba(NO3)2 Balance: F = L + C = 2455.79 kJ/kg H2O
Heat of solution are generally reported as the change in enthalpy associated H2O Bal: F =V+M 4162.22 kg H2O9.2 KCl 1200 kg = 382.92 kg + C;
with the dissolution of a large quantity of solute in excess of pure solvent. 4444.44 = 282.22 + M 100 H2O
=382.92 kg KCl C = 817.08 kg Ba(NO3)2 Solve using three equations three unknowns, but do not
At equilibrium, the heat of crystallization is equal and opposite in sign to the H2O in M = 4162.22
heat of solution. Using the heat of solution at infinite dilution as equal but
use H2O, Solute, and OM Balances as some values cancel
opposite in sign to the heat of crystallization is equivalent to neglecting heat
out and do not give proper answers, must substitute
of dilution. With many materials the heat of dilution is small in comparison enthalpy balance for one of the three
with the heat of solution and the approximation is justified; however, there are
exceptions. Solute Balance:
250=L(0.1625) + C(0.4411);
Solubility and Saturation 3. Pure Na2CO3 10 H2Owas crystallized from a solution containing 25%
Na2CO3 by evaporating 15% of the water at a temperature of 20 oC.
A solution that contains as much of a dissolved solute as it can hold is said to H2O Balance
be saturated with that solute. If a saturated solution is cooled, the solubility of
Calculate the yield of crystals produced per 100 kg of original solution. 750 = V + L(0.8375) + C(0.5589);
the solute decreases, and some solute precipitate in the form of crystals. A
solution in equilibrium with crystals of a solute must be saturated with that Overall Balance
solute. Equilibrium relations for crystallization are expressed in the form of
V= 15% H2O Feed 1000 = V + L + C;
solubility data.
L
crystalline compound containing no water
= 15% (75 kg H2O)
= 11.25 kg H2O Enthalpy Balance:
100 kgFeed 202896 kJ = C(243.36 kJ/kg)+V(2455.79 kJ/kg)
M20degC
Solubility data are ordinarily given as parts by weight of anhydrous crystals
25 kg Na2CO3 at 20 deg C
per 100 parts by weight of total solvent. Solubility data can be presented Solubility = 21.5
efficiently and clearly in phase diagrams, which show equilibrium compositions
75 kg H2O
C (Na2CO3 10 H2O from solute balance
in a system as functions of one or more system variables. The usual phase
diagram for a solid-liquid system is a plot of temperature versus mass fraction xc = mw solute/mw compound L = [250-C(0.4411]/0.1625
of the solid.
105.99
Vacuum Seeded M = F-V (105.99+180) from enthalpy balance
Simple Cooling =25 kg Na2CO3 +75 kg H2O - 11.25 kg H2O xc = 0.3706 V = [202896 kJ - C(243.36 kJ/kg)]/2455.79
= 25 kg Na2CO3;63.75 kg H2O
plug in overall or H2O balance;
C=342.47
Solute Bal : Fxf = Lxl + Cxc
yield = 71.15kg crystals x 100% L=608.85
25 = L(21.5/121.5) + C(0.3076)
V=48.68
100 kg solution
Balance around filter =71.15%
m=L+C
Cxc342.47(0.4411)
(63.75 + 25) = L + C %yield = 100%
Fxf250
C = 88.75-L
%yield=60.42%
back to solute Balance
25 = L(0.176954) + (88.75-L)0.3076
L = 17.6 kg

C = 88.75 kg - 17.6 kg
C = 71.15 kg Na2CO3 10 H2O