From Top to Bottom
Selection Tool - Used for selecting objects (brushes / entities) in all view-ports
Magnify Tool - Used to magnify objects. A mouse scroll-wheel replace this as functional.
Camera Tool - Used to rotate camera in 3D View-port (camera)
Entity Tool - Used to create Entities.
Block Tool - Used to create geometric shapes, also known as brushes.
Texture Application Tool - Used to apply textures to brushes.
Apply Current Texture Tool - Used to apply the currently selected texture to brushes.
Decal Tool - Used to apply decals to surfaces.
Clipping Tool - Used to reshape brushes.
Vertex Tool - Used to manipulate vertex on brushes to redefine the shape.
Path Tool - Used to create paths for AI.
Clipping Tool -
Vertex Tool -
Path Tool -