Ch 22 Bulk Electrolysis: Electrogravimetry and Coulometry Flashcards

1
Q

The two bulk electroanalytical methods

A

electrogravimetry, and
coulometry

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2
Q

In the bulk electroanalytical methods __________ is present

A

Current

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3
Q

Two additional phenomena, ____________, must be considered when current is present.

A

IR drop and polarization

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4
Q

is the rate of charge flow in
a circuit or solution. One ampere of
current is a charge flow rate of one
coulomb per second

A

Current

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5
Q

, the electrical potential
difference, is the potential energy that
results from the separation of charges.

A

Voltage

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6
Q

Ohm’s law:

A

E = IR, or I = E/R.

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7
Q

Ohmic Potential is the product of the resistance R of a cell in ohms (V) and the current I in amperes (A). Also called

A

IR Drop

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8
Q

is current that is
always in one direction, that is, unidirectional.

A

Direct current (dc)

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9
Q

The direction of____________ reverses periodically.

A

alternating
current (ac)

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10
Q

to minimize the IR drop in the cell by having a very small cell resistance (high ionic strength) _____is used

A

three-electrode cell

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11
Q

is the deviation of the
electrode potential from its theoretical
Nernst equation value on the passage
of current.

A

Polarization

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12
Q

is the potential difference between the theoretical
cell potential from Equation 22-2 and
the actual cell potential at a given level
of current.

A

Overvoltage

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13
Q

is the movement of
material, such as ions, from one
location to another

A

Mass transfer

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14
Q

Polarization phenomena can be divided into two categories:

A

concentration polarization and kinetic polarization.

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15
Q

occurs because of the finite rate of mass transfer from
the solution to the electrode surface

A

Concentration polarization

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16
Q

is the movement of a species
under the influence of a concentration
gradient. It is the process that causes
ions or molecules to move from a more
concentrated part of a solution to a
more dilute

A

Diffusion

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17
Q

Reactants are transported to the surface of an electrode by three mechanisms:

A

diffusion, migration, and convection

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18
Q

is the movement of ions
through a solution as a result of
electrostatic attraction between the
electrodes and the ions.

A

Migration

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19
Q

the rate of diffusion and the current become correspondingly larger until the
surface concentration falls to zero, and the maximum or __________ is reached

A

limiting current

20
Q

Migration of analyte species can be
minimized by having a high concentration of an inert electrolyte, called a _____ present in the cell.

A

supporting
electrolyte,

21
Q

is the transport of
ions or molecules through a solution
as a result of stirring, vibration, or
temperature gradients.

A

Convection

22
Q

such as stirring or agitation, tends to decrease the thickness of the diffusion layer at the surface of an electrode and thus decrease concentration
polarization

A

Forced convection,

23
Q

resulting from temperature or density differences also
contributes to the transport of molecules and ions to and from an electrode.

A

. Natural convection

24
Q

The current in a kinetically
polarized cell is governed by the
rate of electron transfer rather
than the rate of mass transfer.

A

kinetic polarization

25
Q

is the current per
unit surface area of the electrode
(A/cm2).

A

Current density

26
Q

is most commonly encountered when the reactant
or product in an electrochemical
cell is gas

A

Kinetic polarization

27
Q

the only practical way of achieving separation of species whose electrode potentials differ by a few tenths of a volt is to measure the cathode potential continuously against a reference electrode whose potential is known. The applied cell potential can then be adjusted to maintain the cathode potential at the desired level. An analysis performed in this way is called a

A

controlled-potential electrolysis.

28
Q

the method where potential of the working electrode is
maintained at a constant level versus a
reference electrode, such as a SCE.

A

potentiostatic method,

29
Q

is the electrode
at which the analytical reaction
occurs.

A

working electrode

29
Q

The voltage applied to the cell is controlled by the variable

A

resistor, R.

30
Q

A ____ is a species that is
easily reduced (or oxidized). It helps
maintain the potential of the working
electrode at a relatively small constant
value and prevents reactions that
would occur under more reducing
or oxidizing conditions.

A

depolarizer

31
Q

A ________- maintains the working
electrode potential at a constant value
relative to a reference electrode.

A

potentiostat

32
Q

is particularly useful for removing easily reduced elements such as copper, nickel, cobalt, silver, and cadmium are separated at this electrode

A

mercury cathode

33
Q

is a potent tool for separating and determining
metallic species having standard potentials that differ by only a few tenths of a
volt.

A

Controlled-potential electrolysis

34
Q

is the amount
of charge required to produce
0.00111800 g of silver metal from
silver ions.

A

coulomb (C)

35
Q

The charge on an electron (and proton) is defined as .

A

1.6022 x 10^19
coulombs (C)

36
Q

A rate of charge flow equal to one coulomb per second

A

one ampere (A) of current

37
Q

Two methods often called the coulometric titrimetry

A

controlled-potential (potentiostatic) coulometry & controlled-current coulometry

38
Q

is also called coulometric titrimetry.

A

Constant-current coulometry

39
Q

One equivalent of chemical change
is the change brought about by

A

1 mol
of electrons

40
Q

The two working electrode of Electrolysis cells for potentiostatic coulometry.

A

(a) platinum-gauze, (b) mercury-pool

41
Q

Coulometric titrations are performed with a constant-current source, sometimes
called a

A

galvanostat

42
Q

Constant-current generators are
sometimes called .

A

galvanostats

43
Q

Detecting the End Point in Coulometric titrations,

A

Potentiometric or
amperometric end points are used in Karl Fischer titrators

44
Q

The constant-current source for a coulometric titration is an electronic device capable of maintaining a current of

A

200 mA

45
Q

Applications of Coulometric Titrations

A

Neutralization Titrations
Precipitation and Complex-Formation Reactions
Oxidation/Reduction Titrations

46
Q

Applications of coulometric titrations

A

Neutralization titration
Precipitation and complex -formation reactions
Oxidation/reduction titration