Because many polymers are composed of primarily of hydrocarbon chains with at most slightly polar functional groups, they tend to have low surface energies and thus adsorb rather poorly. While this can be advantageous for some applications, modification of polymer surfaces is crucial for many other applications in which adhering a substrate to its surface is vital for optimal performance. For example, many applications utilize polymers as structural components, but which degrade rapidly when exposed to weather or other sources of wear. Therefore, coatings must be used which protect the structural layer from damage. However, the poor adhesive properties of nonpolar polymers makes it difficult to adsorb the protective coating onto its surface. These types of problems make the measurement and control of surface energies important to development of useful technologies.
The Gibbs energy of adsorption, , can be determined from the adsorption equilibrium constant:
Because  is negative for a spontaneous process and positive for a nonspontaneous process, it can be used to understand the tendency for different compounds to adsorb to a surface. In addition, it can be divided into a combination of two components:
which are the Gibbs energies of physisorption and chemisorption, respectively. Many polymer applications, such as those which use polytetrafluoroethylene (PTFE, or Teflon) require the use of a surface with specific physisorption properties toward one type of material, while being firmly adhered in place to a different type of material. Because the physisorption energy is so low for these types of materials, chemisorption is used to form covalent bonds between the polymer coating and the surface of the object (such as a pan) which holds it in place. Because the relative magnitudes of chemisorption processes are generally much greater than magnitudes of physisorption processes, this forms a strong bond between the polymer and the surface it is chemically adhered to, while allowing the polymer to retain its physisorption characteristics toward other materials.
Experimentally, the enthalpy and entropy of adsorption are often used to fine-tune the adsorption properties of a material. The enthalpy of adsorption can be determined from constant pressure calorimetry:
where:
: is the heat exchanged,
: is the integral molar enthalpy of adsorption,
: is the number of moles adsorbed.
From the enthalpy of adsorption, the entropy of adsorption can be calculated:
where:
: is the integral molar entropy of adsorption,
: is the temperature in kelvins.
Together, these are used to understand the driving forces behind adsorption processes.