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Achirality means that a molecule is superposable on its mirror image. A reflection plane that leaves the complete labelled spatial structure unchanged establishes achirality. Absence of such a plane alone is not a complete test: other orientation-reversing spatial symmetries can also make a rigid structure achiral.

Chirality means that a molecule cannot be superposed on its mirror image. A carbon attached to four different groups is a common source of chirality; the definition concerns the whole molecule, rather than requiring this particular structural feature.

The test is spatial: apply a translation and a rotation to the entire molecule until corresponding chemical atoms coincide, keeping their identities and chemical bonds. A mirror operation is a reflection; physically turning a model is a rotation. They are different operations. If no such superposition exists, the two forms are enantiomers; if one succeeds, the molecule is achiral. A different-looking flat drawing alone establishes neither conclusion.

For a simple molecule with exactly one tetrahedral stereocenter and four constitutionally different substituents, the mirror forms cannot superpose. Compare entire attached groups, including paths around a ring, rather than just the first chemical atom. Several tetrahedral stereocenters require a whole-molecule check: a meso compound can be achiral. Conversely, axial chirality needs no tetrahedral stereocenter.^[ref]

Why care about this distinction? Two enantiomers can fit differently into an already chiral molecule, just as two opposite hands fit differently into one glove. Thus a protein's spatial arrangement can distinguish a mirror pair even when an achiral measurement cannot. Polarimetry provides a different kind of test: it measures a sample's net optical rotation, which depends on the populations of its enantiomers.

Denote the four displayed matrices, from left to right, by $T_1,T_2,T_3,T_4$. An orthogonal matrix has an orthonormal set of columns, equivalently $T^{T}T=I$. Direct column dot products give $T_j^T{T}_j=I$ for $j=1,2,4$. The first column of $T_3$ has squared Euclidean norm $(1+6+1)/6=4/3$, so the third matrix is the unique nonorthogonal matrix.

For $T_1$, the determinant is $1$. A nonidentity orthogonal transformation of ${\mathbb{R}}^3$ with determinant $1$ is a rotation: it has a fixed axis and restricts to a plane rotation on its orthogonal complement. Consequently $T_1$ is the rotation.

For $T_2$, calculation givesA plane reflection fixes its entire plane, and therefore has eigenvalue $1$. Since $T_2-I$ is invertible, $T_2$ is not a plane reflection. Thus $T_2$ is the combination of a rotation and a reflection. More explicitly, $(1,-2,0{)}^T$ is an eigenvector with eigenvalue $-1$. On the perpendicular plane, $T_2$ is a rotation with $\cos \varphi =2/3$, because $\mathrm{tr}{T}_2=-1+2\cos \varphi =1/3$. This gives a three-dimensional improper orthogonal transformation.

For $T_4$, set $n=(1,2,2{)}^T/3$. ThenThis reflection matrix reverses the normal $n$ and fixes every vector perpendicular to $n$. Therefore $T_4$ is reflection in the plane $x+2y+2z=0$. In particular, $\det T_4=-1$ and $\det (T_4-I)=0$. Finally $T_3$ represents none of the three listed orthogonal transformations, since each preserves the Euclidean norm.

A real orthogonal matrix $T$ of size three with $\det T=-1$ has an eigenvector $n$ of eigenvalue $-1$. Its orthogonal complement is invariant, and the restriction there is an orientation-preserving plane rotation. Thus $T$ is a rotation about the axis $\mathbb{R}n$ composed with a reflection across the plane perpendicular to $n$. Writing the plane angle as $\varphi$, $\mathrm{tr}T=-1+2\cos \varphi$. A pure plane reflection is the case $\varphi =0$; if $\det (T-I)\ne 0$, it cannot be a pure plane reflection.