A system of equations represented by a coefficient matrix $A$ has a unique solution if its determinant is NOT EQUAL to $0$: iff $\det A \neq 0$.
Note that you matrix, below, is an upper triangular matrix. The determinant of a triangular matrix is equal to the product of its diagonal entries:
$$\det A = \det
\begin{bmatrix}
3 & -1 &2 \\
0 & \small\frac53 & \small\frac{14}{3} \\
0 & 0 & a-6 \\
\end{bmatrix}
= 3 \cdot \frac53 \cdot (a - 6)\;=\;5(a-6)$$
$$\det A = 0 \iff a = 6$$
Hence, there exists a unique solution to the system of equations represented by the augmented coefficient matrix if and only if $\;\;\bf{a\neq 0}$:
$$A' =
\left[
\begin{array}{@{}ccc|c@{}}
3&-1&2 & 1 \\
0& \small\frac{5}{3}& \small\frac{14}{3} & \small\frac{10}{3} \\
0&0& a-6 & b-4 \\
\end{array}
\right]
$$
Now we can express $x_3$ as a function of $a$ and $b$ for $a\neq 6:$
The solution, in this case, to $x_3$, is given by $x_3 = \large\frac{b-4}{a-6},\;$ provided $a \neq 6$. It turns out that the precise value of $b$ is irrelevant to the uniqueness of a solution ($b$ may take on any value):
So a unique solution exists to the system of equations given by the augmented coefficient matrix if and only if $$a\in (-\infty, 6)\cup (6, \infty)$$