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Showing posts with label extensive variable. Show all posts
Showing posts with label extensive variable. Show all posts

Monday, August 28, 2023

Composition variables for mixtures

 When composition of a mixture of several gases is to be considered it can be challenging to use all concepts to represent the right quantities. This is a brief explanation.

About mole $n$ and volume $V$

The number of moles for a pure substance is usually represented by $n$. However, for a mixture with several components the moles of each of these components are to be expressed as follows:

$n_1$, $n_2$, $n_3$,...


where the subscripts 1, 2, 3 indicate the component in the mixture. 


Important note: You should remember that moles are extensive variables which is not recommended for composition calculations purposes. You may go around this difficulty dividing $n$ by an intensive variable, which results in a new intensive variable.


On the other hand, you may also have volumetric concentrations [concentración volumétrica] $\bar{c}$ defined as:

$\bar{c}_i=\dfrac{n_i}{V}$


where $n_i$ stands for the mole of some component and $V$ for the volume of the mixture. When $\bar{c}$ is given in units such as mole/l or mole/dm$^3$ the volumetric concentration is also called molar concentration [molaridad].


Important note: volumetric concentration is recommended for liquid or solid mixtures since these change very little with temperature and pressure. However, the use of $\bar{c}_i$ is not advised for gas mixtures. 


Mole ratio $r_i$ and molal concentration $m_i$

This is another form for referring to composition in terms of moles of components in a mixture. Picking up the moles of component 1 as reference we may define the corresponding ratios $r_i$ for all others as:


$r_i=\dfrac{n_i}{n_1}$


On the hand, molal concentration $m_i$ is in fact a variation of the mass concentration (how it is expressed) of the single component  gas $m$. Remember that the mass $m$ can be defined as:


$m=nM$


where $M$ is the molar mass (molalidad) given in [mole/g]. However, the mass of a component in a gas mixture is defined as:


$m_i=\dfrac{n_i}{n_1M_1}=\dfrac{r_i}{M_1}$


In other words, the mass $m_i$ of a mixture component must be given in terms of the mass and moles of the other components.

Since mole and molality ratios are temperature and poressure independent, these are preferable for any physicochemical calcuation.

Mole fractions $x_i$

These are obtained dividing each of the number of moles ($n_1$, $n_2$,...), of each component, by the total number of moles $n_t$ (of the whole substance) which is defined as:


$n_t=n_1+n_2+n_3+...$


The mole fraction is then expressed as,


$x_i=\dfrac{n_i}{n_t}$


Also, the summation of the mole fractions is always equal to 1:


$x_1+x_2+x_3+...=1$


Important note: The composition of a mixture is determined when all mole fractions are given or can be determined. Since mole fractions are temperature and pressure independent, these are suitable, and possibly the most used, to describe the composition of any mixture.


Any question? Write in the comments and I shall try to help.

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Monday, July 17, 2023

Some key basic concepts on thermodynamics

Thermodynamicists tend to use words for technical aspects of this subject. This words are used for other subjects but with some restrictions or further details that help to describe what they are talking about.


Not knowing the meaaning of these concepts would be as trying to comunicate with someone from another country using a different language. This case is not that extreme but difficulties could arise and the worst, you will wste time.

Then, consider the following concepts, presented in a colloquial manner.

Frst, body and system come as words referring to physical things that may be the same for certain circumstances. Perhaps, a difference we can make a first difference between body and system: a system may involve more than one body. In a body and in a system physical and chemical changes, that can be measured, may occur. Next, these measurements, also understood as data, help to describe, in detail, the body or system, or we should say characterized it. Also, the features or parameters to be measured in a body or system may be important due to its changes in time or relation to other features are known as properties.


On the other hand, a system has another feature: it denotes a region or space which is restricted by boundaries with different features such as: thermal conductivity, porosity, etcetera. Measurements of the properties of the system allow to define the system in a given set of conditions, which is called a state. Those properties measured to define the state are also called variables of state

From the mathematical point of view, there are independent and dependent variables. Next, state properties can be expressed as independent variables.

Main components of a function.

On thermodynamics, it is known, empirically, that in order to estimate the intensive variables of a system, only two intensive variables need to be known. An intensive variable is one that does not depend on the amount of matter in the system. If the value of the variable is proportional to the quantity of matter, then it would be an extensive variable.

The equations inoliving independent and dependent variables of state are called state equations

A thermodynamical process implies changes in time of one or more properties. these changes in time can be referred as state changes as well.

Two types of systems can be found. The first ones are closed systems in which mass entrance or leaving is not allowed or never happens. If mass enters or leaves the system, then we would say that the system is open. Similarly, an adiabatic system is a closed system too since no heat is exchanged with the surroundings.

Thermal equilibrium would mean that state variables remain constant boundaries are allowed to change.

Any question? Write in the comments and I shall try to help.

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Ildebrando.

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