July 16, 2007 17:42 00951

Surface Review and Letters, Vol. 14, No. 3 (2007) 461–469

c World Scientific Publishing Company

DETERMINATION OF POINTS OF ZERO CHARGE OF

NATURAL AND TREATED ADSORBENTS

M. NASIRUDDIN KHAN∗ and ANILA SARWAR†

∗
Department of Chemistry, University of Karachi, Karachi 75270, Pakistan
†
Fuel Research Centre, PCSIR Karachi, Karachi 75280, Pakistan
∗
khannasir@myway.com
Received 7 February 2007
Surf. Rev. Lett. 2007.14:461-469. Downloaded from www.worldscientific.com
by MCMASTER UNIVERSITY on 03/10/13. For personal use only.

Although particle size and its measurement are intuitively familiar to particle technologists, the
concept of point of zero charge (pzc) is less widely understood and applied. This is unfortunate
since it is at least as fundamentally important as particle size in determining the behavior of
particulate materials, especially those with sizes in the colloidal range below a micrometer. pzc
is related to the charge on the surface of the particle and strongly depends on the pH of the
material; so it influences a wide range of properties of colloidal materials, such as their stability,
interaction with electrolytes, suspension rheology, and ion exchange capacity.
The pH dependence of surface charges was quantified for four different adsorbent–aqueous
solution interfaces. The points of zero charge were determined for activated charcoal, gran-
ite sand, lakhra coal, and ground corn cob materials using three methods: (1) the pH drift
method, measuring pH where the adsorbent behaves as a neutral specie; (2) potentiometric
titration, measuring the adsorption of H+ and OH− on surfaces in solutions of varying ionic
strengths; (3) direct assessment of the surface charge via nonspecific ion adsorption as a func-
s s
tion of pH. The intrinsic acidity constants for acid and base equilibria, pKa1 and pKa2 , were
also calculated. Lakhra coal was found to have the lowest pzc value among all other adsorbents
studied owing to the presence of a large amount of humus material. The results were used to
explain general connections among points of zero charges, cation exchange capacity, and base
saturation % of adsorbents.

Keywords: Points of zero charge; adsorbent; cationic exchange capacity; surface charge density;
solid–liquid interface.

1. Introduction The surface charge development process is char-

When adsorbents are suspended in an aqueous elec-
trolyte solution, surface electrical charge develops
from the dissociation of the surface hydroxyl groups
and complexation of the background electrolyte ions.
H+ and OH− are considered to be the potential-
determining ions.1 Thus, depending on pH of the
solution and concentration of the electrolyte, these
surfaces can behave as cation exchangers having net
negative charge, or anion exchangers bearing positive
charge or neutral species having no charge.
acterized by an important interfacial parameter,
commonly known as point of zero charge (pzc). The
concept of pzc was born during the studies of the floc-
culation of hydrophobic colloids.2 In the first remark-
able series of papers published in Croatica Chemica
Acta, Stumm et al.3 invoked the pzc to express the
acid–base reactions of hydroxyl groups on the surface
of oxide minerals. Nearly 30 years after their pioneer
work, the prediction of the surface charge properties
of amphoteric adsorbents through chemical models of
the particle–water interface has become a hot topic

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