Surface Chemistry • Topic 3 of 3

Colloids

A colloid is a heterogeneous system in which one substance (the dispersed phase) is spread as fine particles through a continuous medium (the dispersion medium). Particle size is the key. In a true solution particles are smaller than $1\ \text{nm}$, the system is one phase, transparent, passes through filter paper and parchment, and does not scatter light. In a colloid particle size is $1$–$1000\ \text{nm}$, the system is two-phase, passes through ordinary filter paper but not parchment, and scatters light. In a suspension particles are larger than $1000\ \text{nm}$, are visible, settle on standing and are retained by filter paper.

Classification. By the affinity of the dispersed phase for the medium, sols are lyophilic (solvent-loving, e.g. starch, gum, gelatin in water — reversible and very stable) or lyophobic (solvent-hating, e.g. sols of metals and metal sulphides — irreversible and needing a stabiliser). By particle type they are multimolecular (aggregates of many small atoms/molecules, e.g. gold sol, sulphur sol), macromolecular (single large molecules, e.g. proteins, starch, cellulose, plastics) or associated colloids / micelles (substances behaving as normal electrolytes at low concentration but forming aggregates above the critical micelle concentration, e.g. soaps and detergents). By physical state of the two phases we get sols, gels, aerosols, foams and emulsions; e.g. fog is a liquid-in-gas aerosol, milk is a liquid-in-liquid emulsion, and cheese is a liquid-in-solid gel.

Preparation. Lyophilic sols form simply by mixing the substance with the medium. Lyophobic sols are made by condensation methods (building particles up to colloidal size — oxidation, reduction, hydrolysis or double decomposition, e.g. $\text{FeCl}_3$ + hot water gives a $\text{Fe(OH)}_3$ sol) or by dispersion methods (breaking large particles down, e.g. Bredig's arc for metal sols and peptisation, the conversion of a fresh precipitate into a sol by adding a small amount of a suitable electrolyte). Purification removes excess electrolyte by dialysis (diffusion of small ions through a parchment membrane), electrodialysis (dialysis speeded by an applied potential) or ultrafiltration.

Properties. The Tyndall effect is the scattering of a beam of light by colloidal particles, making the path of the beam visible; it distinguishes a colloid from a true solution. Brownian motion is the continuous zig-zag movement of colloidal particles caused by unequal bombardment by molecules of the medium; it keeps particles suspended. Electrophoresis is the movement of charged colloidal particles toward an oppositely charged electrode under an applied field, proving that colloidal particles carry charge. The charge arises from preferential adsorption of ions and gives stability through mutual repulsion; the layer of adsorbed ions plus the oppositely charged layer is the electrical double layer (zeta potential).

Coagulation (or flocculation) is the aggregation and settling of colloidal particles, brought about by adding an electrolyte, by mutual mixing of oppositely charged sols, by heating or by prolonged dialysis. The Hardy-Schulze rule states that the coagulating power of an ion increases sharply with its charge: the effective ion is the one carrying the charge opposite to that of the sol. For a negative sol (e.g. $\text{As}_2\text{S}_3$) the order is $\text{Al}^{3+}>\text{Ba}^{2+}>\text{Na}^+$; for a positive sol (e.g. $\text{Fe(OH)}_3$) it is $[\text{Fe(CN)}_6]^{4-}>\text{PO}_4^{3-}>\text{SO}_4^{2-}>\text{Cl}^-$.

Emulsions are colloidal dispersions of one liquid in another immiscible liquid. The two types are oil-in-water (o/w, e.g. milk, vanishing cream) and water-in-oil (w/o, e.g. butter, cold cream). They are stabilised by emulsifiers (soaps, detergents, proteins) and can be broken by heating, centrifuging or adding an electrolyte (demulsification). Applications of colloids include water purification by alum (coagulating the negatively charged clay sol), the Cottrell electrostatic precipitator for removing carbon/dust from smoke, formation of deltas where river (colloidal clay) meets sea (electrolyte), cleansing action of soaps (micelle formation), and many foods, medicines and rubber/tanning processes.

Tyndall effect — scattering of light by a colloidal soltrue solutioncolloidal solscattered beam is visible (Tyndall cone)
1
Worked Example
Give two points of difference between a true solution and a colloidal solution.
Solution
  1. Particle size: less than $1\ \text{nm}$ in a true solution; $1$–$1000\ \text{nm}$ in a colloid.
  2. Tyndall effect: a true solution does not scatter light; a colloid shows the Tyndall effect.
  3. (Also: a true solution is one-phase and passes through parchment; a colloid is two-phase and does not.)

Answer: A colloid has larger particles ($1$–$1000\ \text{nm}$) and shows the Tyndall effect, unlike a true solution.

2
Worked Example
Distinguish between lyophilic and lyophobic colloids.
Solution
  1. Lyophilic sols have a strong affinity of the dispersed phase for the medium; lyophobic sols have little affinity.
  2. Lyophilic sols are reversible and self-stabilised; lyophobic sols are irreversible and need a stabiliser.
  3. Examples: starch, gum, gelatin (lyophilic); sols of gold, silver, $\text{As}_2\text{S}_3$ (lyophobic).

Answer: Lyophilic = solvent-loving, reversible, stable; lyophobic = solvent-hating, irreversible, need a stabiliser.

3
Worked Example
What is peptisation? Give an example.
Solution
  1. Peptisation is the conversion of a freshly prepared precipitate into a colloidal sol.
  2. It is done by adding a small amount of a suitable electrolyte (the peptising agent).
  3. The added ions are adsorbed, giving the particles charge and breaking the precipitate into colloidal particles.
  4. Example: a precipitate of $\text{Fe(OH)}_3$ is peptised to a sol by adding a little $\text{FeCl}_3$.

Answer: Peptisation is making a sol from a fresh precipitate using an electrolyte, e.g. $\text{Fe(OH)}_3$ with $\text{FeCl}_3$.

4
Worked Example
State the Hardy-Schulze rule and arrange $\text{Na}^+$, $\text{Ba}^{2+}$ and $\text{Al}^{3+}$ in order of coagulating power for a negative sol.
Solution
  1. The Hardy-Schulze rule: the coagulating power of an ion increases with its charge, and the effective ion carries the charge opposite to that of the sol.
  2. For a negative sol the positive (cation) coagulates it.
  3. Higher charge means greater coagulating power, so $\text{Al}^{3+}>\text{Ba}^{2+}>\text{Na}^+$.

Answer: Coagulating power rises with ionic charge; $\text{Al}^{3+}>\text{Ba}^{2+}>\text{Na}^+$.

5
Worked Example
Why does the sky appear blue and why does a beam of sunlight become visible in a dusty room?
Solution
  1. Both are examples of the Tyndall effect — scattering of light by colloidal-sized particles.
  2. Dust and water droplets in the air act as colloidal particles and scatter sunlight.
  3. Blue (shorter wavelength) light is scattered more strongly than red, so the scattered sky light looks blue.
  4. In a dusty room the scattered light makes the path of the beam visible.

Answer: Both are due to the Tyndall effect — scattering of light by colloidal particles in the air.

6
Worked Example
Name the two types of emulsion with one example of each, and state how an emulsion is stabilised.
Solution
  1. Oil-in-water (o/w): oil dispersed in water; example, milk or vanishing cream.
  2. Water-in-oil (w/o): water dispersed in oil; example, butter or cold cream.
  3. Emulsions are stabilised by adding an emulsifier (emulsifying agent) such as soap, detergent or protein.

Answer: o/w (e.g. milk) and w/o (e.g. butter); stabilised by an emulsifier like soap or protein.

Key Points

  • Colloids have particle size $1$–$1000\ \text{nm}$ (true solution $<1\ \text{nm}$, suspension $>1000\ \text{nm}$); a colloid is two-phase and shows the Tyndall effect.
  • Classification: lyophilic (reversible, self-stable) vs lyophobic (irreversible, need a stabiliser); multimolecular, macromolecular and associated (micelle) colloids; and by physical state (sol, gel, aerosol, foam, emulsion).
  • Lyophobic sols are prepared by condensation (oxidation/reduction/hydrolysis, e.g. $\text{FeCl}_3$ + hot water) or dispersion (Bredig's arc, peptisation), and purified by dialysis, electrodialysis or ultrafiltration.
  • Key properties: Tyndall effect (light scattering), Brownian motion (zig-zag motion keeping particles suspended) and electrophoresis (charged particles migrate to an electrode).
  • Coagulation follows the Hardy-Schulze rule (coagulating ion is opposite in charge to the sol and more effective the higher its charge); emulsions are o/w (milk) or w/o (butter), stabilised by emulsifiers.
Tap an option to check your answer0 / 4
Q1.The particle size range of a colloidal solution is about:
Explanation: Colloidal particles are $1$–$1000\ \text{nm}$; below $1\ \text{nm}$ is a true solution and above $1000\ \text{nm}$ is a suspension.
Q2.The scattering of light by colloidal particles, making the beam path visible, is called:
Explanation: The Tyndall effect is the scattering of light by colloidal particles; it distinguishes a colloid from a true solution.
Q3.According to the Hardy-Schulze rule, the most effective ion in coagulating a negatively charged sol is:
Explanation: A negative sol is coagulated by cations, and the higher the charge the greater the power, so $\text{Al}^{3+}$ is most effective.
Q4.Purification of a colloidal sol by diffusion of dissolved ions through a parchment membrane is called:
Explanation: Dialysis removes excess electrolyte from a sol by allowing only small ions to diffuse out through a parchment/semipermeable membrane.