8.9 Stability and coagulation of colloids

1) Stability of colloids

Colloids, a dispersion system with high specific area and

thus high interfacial specific energy, is thermodynamically

unstable.

Collision between colloidal particles frequently occur and

aggregation is always a possibility.

Stabilizing factors:

Dynamic stabilization: Brownian motion and diffusion

prevents colloidal particles from sedimentation.

Electric stabilization: All the colloid particles in a particular

system have the same charge tends to repulse each other and

keep the colloid in suspension.

Solvation shell: The interaction between particle and solvent

also helps to prevent aggregation of colloidal particles on

collision.

2) Precipitation of colloids by electrolytes

Precipitating value and precipitating efficiency / power

Precipitating value:

The lowest concentration of electrolyte (usually in mmol

dm-3) at which precipitation of colloid can be easily

observed.

A lyophobic colloid is very sensitive to the addition of a

small amount of an electrolyte.

Electrolytes As2S3 () Electrolytes Al(OH)3(+)

LiCl 58 NaCl 43.5

NaCl 51 KCl 46

KCl 49.5 KNO3 60

CaCl2 0.65 K2SO4 0.30

MgCl2 0.72 K2Cr2O7 0.63

MgSO4 0.81 (KOOC)2 0.69

AlCl3 0.093 K3[Fe(CN)6] 0.08

Al(NO3)3 0.095

Precipitating value of different electrolytes towards the same colloids

Hardy-Schulze rules.

The ion which is effective in causing precipitation of a sol is the

one whose charge is of opposite sign to that of the colloidal

particles, i.e., counterions

(1) Valence:

the higher the valence, the lower the precipitating value.6 6 6I II III 1 1 1

M : M : M : : 100 :1.6 : 0.31 2 3

is only valid without specific adsorption.

The precipitating efficiency of morphia (I) chloride is larger than

Mg (II) and Ca (II)

(2) radius

Hofmeister / lyotropic series

H+ > Cs+ > Rb+ > NH4+ > K+ > Na+ > Li+

F- > Cl- > Br- > NO3- > I-

(3) co-ions When counterion is the same, the higher the valence of the co-ions, the higher the precipitating value.

Electrolytes KNO3 ½ K2SO4

Precipitating values 50 65.5

Precipitating values for As2S3 colloids

Fe(OH)3 sol + HClNonregular aggregation

Aggregation of sols by electrolytes

1) Preparation of soy-bean curd.

2) Detoxification of heavy metal ions

3) Formation of delta and alluvion

When the river water containing colloidal clay flows into the sea, the

brine induces coagulation. This is a major cause of silting in estuaries.

Aggregation of sols by electrolytes

4) mutual precipitation of colloids

Generally, mixing of colloids with the same charge does not lead to precipitation, while mixing of colloids with different charge will result in mutual precipitation.

Fe(OH)3(3.04 g dm-3) 9 8 7 5 3 2 1 0.2

As2S3(2.07 g dm-3) 1 2 3 5 7 8 9 9.8

charge + + + + 0 - - -

phenomenon --- Turbid ---

Purification of water using alum

Coagulation

Coagulation is the process of adding chemicals to water to

make dissolved and suspended particles bind together

(coagulate) and form larger particles (flocculant) that settle

out of the water.

Aluminum sulphate, ferric sulphate, ferric chloride, and

forms of aluminum or iron salts called polymers are all

suitable coagulation chemicals approved for water

treatment.

5) effect of macromolecules on colloids

1) Stabilization effect:

When lyophilic sol, such as gelatin, albumin, agar, casein, gum arabic, glue, starch, etc. is added to a sol, the latter may be prevented from precipitation by electrolytes. Such macromolecules are named as stabilizing agent or stabilizers.

The macromolecules adsorbed on the colloidal particle form a tough shell which helps to keep the particle apart.

Gold number:

the number of milligrams of the protective colloid that just prevents the change of color when 1 cm3 of the standard salt solution (10 % NaCl) is added to 10 cm3 of the standard gold sol (0.006 %). (By Zsigmondy)

Protective colloids Gold number / mg

Gelatin (明胶 ) 0.005-0.01

Albumin (白蛋白 ) 0.1-0.2

Gum arabic 0.15-0.5

Dextrin (糊精 ) 6.0-20.0

Potato starch 25

Red number: Congo red

2) Sensitization effect: When small amount of some lyophilic sols was added into a lyophobic sol, the sol can be precipitated by less amount of an electrolyte. In other words, the addition of the lyophilic sols decrease the precipitating value of the sol. This phenomenon is named as sensitization.

The recoil of the macromolecules helps to draw several particles together.

LaMer: Bridging effect

Flocculation of colloids:

flocculants

Chemicals by adding which suspended solids in the wastewater are sedimented and clearized water is gotten.

Kinds of flocculants:

1. inorganic: polyalminum chloride

2. polymers: polyacrylic acid, polyacrylamide derivatives

3. naturally occurring flocculants: chitosan, sodium arginate

Polymeric electrolyte – polyacrylamide (PAM)

M > 106

-[- CH2 – CH-]m-

C=O

NH2

Differences in flocculation and aggregation

flocculants are widely used in water treatment plant, pulp

industries ,the food industries and so on.,

Coagulation treatment improved the water quality by

1. reducing the dissolved organic carbon (DOC) concentration

by about 60%;

2. reducing color by over 80%;

3. reducing the dissolved phosphate concentrations by as

much as 99%;

4. reducing nutrient availability;

5. reducing the alkalinity and pH of the water.

The electrolyte causes a compression of the diffusion layer

of the double layer and decreases electrokinetic potential,

which allows two particles to make a closer approach to each

other.

6) DLVO theory

6 6 6I II III 1 1 1

M : M : M : : 100 :1.6 : 0.31 2 3

Around 1942, Deijaguin-Landao-Verwey-Overbeek

1) The inter-particle attraction: long-range dispersion forces

x

aHVa 12

22203

4nhH Hamaker constant

2) The inter-particle repulsion:

xr e

KTnV

22064 Debye-Hückel

constantkT

en

208

xar erKV 00

The inter-particle potential

x

aHerKx xa

12)( 00

x

aHerKx xa

12)( 00

Interparticle potential curve Potential curves for colloidal systems with different .

x

E

0

x

E

0

62

453

c ZH

rkTC

)(

As the concentration of electrolyte increases, of colloid decreases.

When = 0.03 V, colloid begins to

settle. When = 0, precipitation rate

attains maximum.

/V

0.03 0.00

r

c/mmol/L