Bipolar membrane

Bipolar membranes are a special type of layered ion exchange membrane. They consist of two
polymer layers carrying fixed charges; one is only permeable for the anions and the other only
for cations. Actually, unlike with membranes used for separation purposes, nothing should be
transported from one side to the other. The desired function is a reaction in the bipolar junction
of the membrane where the anion and the cation permeable layers are in direct contact: water is
split into hydroxide ions and protons by a disproportionation reaction. The produced hydroxide
ion and proton are separated by migration in the respective membrane layer out of the
membrane. Unlike water splitting at electrodes during electrolysis, no gases are formed as a side
product to this reaction, nor are gases used up.
Electrodialysis with bipolar membranes (ED-BPM) can replace electrolysis with water splitting
at the electrodes but has a wider variety of applications. ED-BPM can be used to produce acids
and bases from a neutral salt as described in more detail below. It is a membrane reactor process
where a reaction and a separation occur in the same unit or even in the same membrane water
splitting without gases involved in the reaction is only possible when the reaction products are
separated immediately, otherwise the reverse reaction, a recombination to water, cannot be
prevented.
Bipolar membrane function
The function of a bipolar membrane can be explained by looking at the concentration profiles in
the membrane during operation, Figure . the bipolar membrane consists of two ion exchange
layers of opposite charge in intimate contact. In the applied electric field, the hydroxide ions and
the protons produced in bipolar junction move towards the respective electrode in the electric
field. Water is replenished in the interface by diffusion through the gel-like membrane layers.
According to the respective interface equilibrium with the surrounding solutions, not only
hydroxide ions and protons but also the acid anions and the base cations are present in the
membrane phase. This leads to the undesired transport of these anions and cations across the
membrane. The driving forces for the transport of these ions are both, the electrical potential and
the concentration gradients. The water splitting requires energy that is supplied by the applied
electrical field.

The separating feature of the membrane layers is mainly necessary to prevent ions of the same
charge as the fixed charge (co-ions) from reaching the reactive bipolar junction and to allow the
produced ions of the opposite charge (counter-ions) to move out of the membrane. This holds
also for the extra membranes in the module.

Schematic concentration profile in a bipolar membrane in contact with an acid and a base on
its two sides
Bipolar membranes are often modelled as homogeneous phases but most membranes are actually
heterogeneous, similar to the simpler cation and anion permeable membranes . For EDmembranes, only few transport descriptions start to be applied for transport in heterogeneous
membranes. For modelling, pressure terms may be negligible in first approximations because the
fluids are non-compressible. However, the stagnant membrane phase can expand and the
transport properties of the membrane can change. One indication of that is the change of water
content with changed solution concentrations or different counter ion for the fixed charges.
For the description of transport in bipolar membranes as well as other ion permeable membranes,
two somehow different approaches are possible. Mostly the phenomenological description with
the extended Nernst-Planck equations is used because it relates measurable physical properties
such as an electric potential difference or concentration gradients directly to ion fluxes. However,
it suffers from the fact that the main transport parameters, the ion diffusion coefficients, are not

fixed values but depend on the entity of the environment the ion encounters. In the other
description, based on the Maxwell-Stefan approach, binary diffusion coefficients or friction
coefficients are used between all the pairs of the substances present in the system. The MaxwellStefan description has the advantage that the binary diffusion coefficients are constant over wider
concentration ranges, however, they need to be determined for all the binary interactions between
the species present in the system. Some of these are not directly accessible, the determination
and interpretation is not straight-forward for all binary pairs .
Limitations
With the function of a bipolar membrane in the electrodialysis module , it is clear that the
limitations of the bipolar membrane itself form limitations of the bipolar membrane
electrodialysis process. The main limitations are
(1) the chemical stability, especially against the concentrated base on its anion permeable side,
(2) the co-ion transport, and
(3) the membrane layer resistance against ion transport. Other factors influencing its behaviour
are the catalyst stability, the possibility to withstand the increased pressure in the membrane
when hydroxide ions and protons recombine to water as soon as the current is switched off, and
an eventual poisoning or scaling of the membrane by complex formation of the fixed charge with
multivalent metal salts. Also a reduced water content is not favourable at high current densities,
the water used up in the water splitting reaction has to be replenished through diffusive transport
across the membrane layers. These limitations are subject of the chapters of this thesis. In the
following, after short economical considerations, an overview is presented how these limitations
can be approached.