This study is concerned with the determination of the molar heat capacity, Cp, and molar heat of mixing ,HE, of aqueous 2-(Propylamino)ethanol (PAE), 2-(Butylamino)ethanol (BAE), 1-(2-Hydroxyethyl)piperidine (HEP), and Bis(2-methoxyethyl)amine (BMOEA) solutions, as well as the Cp of 2-(Ethylamino)ethanol (EAE) and HE of aqueous Diglycolamine (DGA) using a C80 heat flow calorimeter over a full range of mole fractions (x1). Cp measurements were performed in a temperature range of 303.15K to 353.15K, while HE measurements were performed at three temperatures (298.15, 313.15, and 333.15 K). Of the five alkanolamines studied, BMOEA and BAE exhibited the highest values of heat capacity, whereas EAE had the lowest values. Cp increased with an increase in the size of the alkyl group. Primary amines had the highest contribution, followed by secondary and tertiary amines. Straight chains showed higher Cp values than the cyclic alkyl groups. Hydroxyl groups led to lower Cp than ether groups. The CpE data, partial molar excess quantities and the reduced molar excess heat capacity functions, CpE/(x1x2), were calculated at several temperatures and correlated as a function of x1 employing the Redlich-Kister expression (RK). Percentages of relative deviation (% RD) from all the predicted heat capacity data for the Group Additivity Analysis and Molecular Connectivity Analysis were found to be within 1.83 and 2.64 %, respectively. Hydrogen bonding plays a major role within the interactions present in aqueous solutions of alkanolamines; stronger bases reacted more with water. Excess enthalpies increased with an increase in the size of the carbon chain. Cyclic alkyl groups had lower HE than straight chains. Tertiary amines had the lowest values, followed by secondary and primary amines. Ether groups exhibited stronger H-bonding with water than the hydroxyl groups. Excess enthalpies of amines and water at infinite dilution were calculated from the coefficients of the Redlick Kister equations. The modified UNIFAC model regressed the data with the lowest Percentage Relative Deviations (≤1%).