If the constituents of a mixture  are completely miscible in all proportions with each other, the type of azeotrope is called a homogeneous azeotrope. Homogeneous azeotropes can be of the low-boiling or high-boiling azeotropic type. For example, any amount of ethanol can be mixed with any amount of water to form a homogeneous solution.
If the components of a mixture are not completely miscible, an azeotrope can be found inside the miscibility gap. This type of azeotrope is called a heterogeneous azeotrope or heteroazeotrope.  A heteroazeotropic distillation will have two liquid phases. Heterogeneous azeotropes are only known in combination with temperature-minimum azeotropic behavior. For example, if equal volumes of chloroform (water solubility 0.8 g/100 ml at 20 °C) and water are shaken together and then left to stand, the liquid will separate into two layers. Analysis of the layers shows that the top layer is mostly water with a small amount of chloroform dissolved in it, and the bottom layer is mostly chloroform with a small amount of water dissolved in it. If the two layers are heated together, the system of layers will boil at 53.3 °C, which is lower than either the boiling point of chloroform (61.2 °C) or the boiling point of water (100 °C). The vapor will consist of 97.0% chloroform and 3.0% water regardless of how much of each liquid layer is present provided both layers are indeed present. If the vapor is re-condensed, the layers will reform in the condensate, and will do so in a fixed ratio, which in this case is 4.4% of the volume in the top layer and 95.6% in the bottom layer.
Combinations of solvents that do not form an azeotrope when mixed in any proportion are said to be zeotropic. Azeotropes are useful in separating zeotropic mixtures. An example is acetic acid and water, which do not form an azeotrope. Despite this, it is very difficult to separate pure acetic acid (boiling point: 118.1 °C) from a solution of acetic acid and water by distillation alone. As progressive distillations produce solutions with less and less water, each further distillation becomes less effective at removing the remaining water. Distilling the solution to dry acetic acid is therefore economically impractical. But ethyl acetate forms an azeotrope with water that boils at 70.4 °C. By adding ethyl acetate as an entrainer, it is possible to distill away the azeotrope and leave nearly pure acetic acid as the residue.