Boiling Points of Alkanes

Reminder about Alkanes:

Alkanes are chemical compounds that consist only of the elements carbon (C) and hydrogen (H) in proportions according to the general formula: C_nH_(2n+2) where the letter n represents the number of carbon atoms in each molecule. The atoms that form alkanes are linked exclusively by single bonds, hence alkanes are saturated hydrocarbons.

There are three main types of alkanes: Linear alkanes, branched alkanes and cyclic alkanes (which may also be referred to as cycloalkanes).

Definitions of Boiling Point:

There are some other precise definitions of boiling points used in particular situations, such as:

Notes:

1. As boiling points are temperatures they may be expressed in degrees Fahrenheit, degrees Celsius or degrees Kelvin.
   When stating boiling points remember to specify the units - without which a number alone is meaningless.
2. Boiling versus Evapouration :
   Liquids can change state to vapors (gases) at temperatures below the boiling point of the substance via the process of evaporation, which is a surface effect in which molecules located near the vapor / liquid surface escape into the vapor (gas) phase. This is in contrast to the process of boiling in which molecules of the substance located anywhere in the liquid - including well below its surface - escape, by forming vapor bubbles within the liquid, which then rise to the surface to leave the liquid phase.

Table of Boiling Points of Linear Alkanes:

Note: In the case of the names of alkanes beginning with n- , the n- part is included to specify the linear (as opposed to a branched or cyclic) form of that particular alkane. Recall that in some cases the atoms forming alkanes may be arranged in different ways, hence the alkane may exist in the forms of several different structural isomers. * The figures above have been found cited by several sources and are believed to be representative - but have not been verified experimentally by or for this website. *

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Chart of Boiling Points plotted against Number of Carbon Atoms in Linear Alkanes:

One way to consider the trend in boiling points across the homologous series of linear alkanes is by plotting temperatures of the boiling point against number of carbon atoms in each linear alkane. The following chart of boiling points of alkanes against the number of carbon atoms in each linear alkane includes values for larger alkanes with up to 50 carbon atoms.

Discussion of Chart of melting and boiling points of alkanes:

1. Actual values plotted on the above chart are represented by red squares (in the case of boiling points) and green triangles (in the case of melting points). Values have been plotted for each of the first 12 linear alkanes and also for linear alkanes with each of 20, 30, 40 and 50 carbon atoms.
2. The dotted lines in red (between the points representing boiling points) and in green (between the points representing melting points) indicate likely approximate values for the alkanes with numbers of carbon atoms in their chains for which specific values were not available with which to draw the chart.
3. Why include both melting points and boiling points ?
   There are three main states of matter: solid, liquid and gas.
   Plotting both melting points and boiling points on the same graph enables one to use the graph to decide if a particular linear alkane (position along the x-axis) is likely* to be a solid, liquid or gas at any particular temperature (position along the y-axis).
   * We cannot draw absolutely accurate conclusions about states of matter from this graph because boiling points vary according to pressure as well as temperature and the information on the above graph does not mention pressures, or even include actual values for all linear alkanes.
   
   Example: What is the state (solid, liquid or gas) of each alkane compound at 20^oC ?
   A dashed line is shown to represent the condition "temperature = 20^oC", which is a useful temperature to discuss because room temperature is typically around 20^oC.
   
   At 20^oC :
   • The red line (representing boiling points) is below the dashed black line (representing temperature = 20^oC) for values of n="number of carbon atoms forming the linear alkane chain" < 5.
     Hence for values n=1 to 4 (methane, ethane, propane and butane), those linear alkanes are likely to be a gas at approx. 20^oC.
   • The dashed black line (representing temperature = 20^oC) is between the red line (representing boiling points) above it, and the green line (representing melting points) below it, for values of n="number of carbon atoms forming the linear alkane chain" of between n=5 (pentane) and n=17.
     Hence for values of n=5 to 17, the linear alkane is likely to be a liquid at approx. 20^oC.
   • The green line (representing melting points) is above the dashed black line (representing temperature = 20^oC) for values of n="number of carbon atoms forming the linear alkane chain" > approximately 17.
     Hence for values of n=18 and above, the linear alkane is likely to be a solid at approx. 20^oC.
     
     
4. The shapes of the red line (representing boiling points) and the green line (representing melting points)
   describe visually the trends, that is - how boiling points and melting points vary with n="number of carbon atoms forming the linear alkane chain" in the range of values shown. In general such trends can also be described mathematically by equations describing the curve that best fits each series of points - not required for UK GCSE Chemistry.
5. Why only plot resuts for Linear Alkanes ?
   This is a simplification to make the chart easier to explain and discuss.
   The boiling (and melting) points of branched alkanes differ from those of linear alkanes. Recall that alkanes that include 4 or more carbon atoms show structural isomerism, meaning that there are two or more different structural formulae that you can draw for each molecular formula. Each isomer has a different melting and boiling point. As the number of carbon atoms in alkanes increase the number of different isomers increases dramatically. To give an indication of the variation in boiling points of different isomers of the same alkane, cycloalkanes have boiling points typically around 10^oC to 20^oC higher than the corresponding linear alkane.