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Matrix representation of linear systems
A linear system can be written compactly as a single matrix equation
$$A\mathbf x=\mathbf b.$$
Here $A$ contains the coefficients, $\mathbf x$ contains the unknowns and $\mathbf b$ contains the constant terms.
From equations to matrices
The system
$$\begin{aligned} 2x+y&=5,\ -x+3y&=4 \end{aligned}$$
becomes
$$\begin{pmatrix} 2&1\ -1&3 \end{pmatrix} \begin{pmatrix}x\y\end{pmatrix}
\begin{pmatrix}5\4\end{pmatrix}.$$
Multiplying the matrix by the vector reproduces the two original equations.
Coefficient and augmented matrices
The coefficient matrix is
$$A=\begin{pmatrix}2&1\-1&3\end{pmatrix}.$$
For solving the system, the coefficients and constants can be placed together in the augmented matrix
$$\left[\begin{array}{cc|c} 2&1&5\ -1&3&4 \end{array}\right].$$
The vertical bar is only a visual separator; it keeps the constant column associated with the equations while row operations are performed.
Matrix notation removes repeated variable names and exposes the structure that Gaussian elimination will manipulate.