Chapter 19: Potentiometry Flashcards
are based on measuring the potential of
electrochemical cells without drawing appreciable current
potentiometric methods
The equipment for potentiometric methods is simple and inexpensive and includes a
reference electrode
indicator electrode
potential-measuring device
is a half-cell having a known electrode potential that remains constant at constant temperature and is independent of the composition of the analyte solution.
reference electrode
has a potential that varies in a known way
with variations in the concentration
of an analyte.
indicator electrode
TRUE or FALSE
Potassium chloride is a nearly ideal electrolyte for the salt bridge because the mobilities of the K1 ion and the Cl2 ion are nearly equal.
TRUE
TRUE or FALSE
The ideal reference electrode has a potential that is accurately known, constant, and
completely insensitive to the composition of the analyte solution. In addition, this
electrode should be rugged, easy to assemble, and should maintain a constant potential
while passing minimal currents.
TRUE
consist of mercury in contact with a solution that is saturated with mercury(I) chloride (calomel) and that also contains a known concentration of potassium chloride.
calomel reference electrodes
mercury (I) chloride is also known as
calomel
is available as translucent flakes, is a
heteropolysaccharide that is extracted
from certain East Indian seaweed.
Solutions of _____ in hot water set to a
gel when they are cooled.
agar
what kind of reference electrode is the most widely marketed reference electrode system that consists of a silver electrode immersed in a solution of potassium chloride that has been saturated with silver chloride
silver/silver chloride reference electrodes
TRUE or FALSE
Silver/silver chloride electrodes have the advantage that they can be used at temperatures greater than 60C, while calomel electrodes cannot
TRUE
When two electrolyte solutions of different compositions are in contact with one
another, there is a potential difference across the interface. It is the result of an unequal distribution of cations and anions across the boundary due to differences in the rates at which these species diffuse
liquid junction potentials
TRUE or FALSE
The magnitude of the liquid junction potential can be minimized by placing a salt bridge between the two solutions. The salt bridge is most effective if the mobilities of the negative and positive ions in the bridge are nearly equal and if their concentrations are large
TRUE
responds rapidly and reproducibly to changes in the concentration of an analyte ion (or group of analyte ions).
ideal indicator electrode
types of indicator electrode
metallic
membrane
ion-sensitive field effect transistors
classification of metallic indicator electrodes
electrodes of the first kind,
electrodes of the second kind, and
inert redox electrodes.
is a pure metal electrode that is in direct equilibrium with its cation in the solution. single reaction is involved
electrodes of the first kind
TRUE or FALSE
Electrode systems of the first kind are not widely used for potentiometric determinations for several reasons. For one, metallic indicator electrodes are not very selective and respond not only to their own cations but also to other more easily reduced
cations.
TRUE
Metals not only serve as indicator electrodes for their own cations but also respond to the activities of anions that form sparingly soluble precipitates or stable complexes with such cations.
electrodes of the second type
TRUE or FALSE
the most convenient method for determining pH involves measurement of the potential that appears across a thin glass membrane that separates two solutions with different hydrogen ion concentrations.
TRUE
are sometimes called p-ion electrodes because the data obtained from them are usually presented as p-functions, such as pH, pCa, or pNO3
membrane electrodes/ membrane indicator electrodes
contains two reference electrodes: the external calomel electrode and
the internal silver/silver chloride electrode.
glass electrode system
TRUE or FALSE
The potentials of the two reference electrodes depend on the
electrochemical characteristics of their respective redox couples, but the potential across the glass membrane depends on the physicochemical characteristics of the glass and its response to ionic concentrations on both sides of the membrane
TRUE
Glasses that absorb water are said to
be
hygroscopic
TRUE or FALSE
The two surfaces of a glass membrane must be hydrated before it will function as a pH electrode. Nonhygroscopic glasses show no pH function. Even hygroscopic glasses lose their pH sensitivity after dehydration by storage over a desiccant
TRUE
varies with the pH of the analyte solution
boundary potential
components of potential glass electrode
boundary potential
potential of the internal Ag/ AgCl reference electrode
small asymmetry potential
It consists of a conducting membrane that selectively binds calcium ions, an internal solution containing a fixed concentration of calcium chloride, and a silver electrode that is coated with silver chloride to form an internal reference electrode
Liquid membrane electrodes
is a measure of a response of an ion-selective electrode to other ions.
selectivity coefficient
TRUE or FALSE
The sensitivity of the liquid-membrane electrode for calcium ions is reported to be 50 times greater than for magnesium ion and 1000 times greater than for sodium or potassium ions.
TRUE